TWI819096B - Double sided adhesive tape - Google Patents
Double sided adhesive tape Download PDFInfo
- Publication number
- TWI819096B TWI819096B TW108133943A TW108133943A TWI819096B TW I819096 B TWI819096 B TW I819096B TW 108133943 A TW108133943 A TW 108133943A TW 108133943 A TW108133943 A TW 108133943A TW I819096 B TWI819096 B TW I819096B
- Authority
- TW
- Taiwan
- Prior art keywords
- double
- adhesive tape
- resin layer
- sided adhesive
- weight
- Prior art date
Links
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 114
- 229920005989 resin Polymers 0.000 claims abstract description 226
- 239000011347 resin Substances 0.000 claims abstract description 226
- 239000010410 layer Substances 0.000 claims abstract description 178
- 239000006260 foam Substances 0.000 claims abstract description 127
- 239000000463 material Substances 0.000 claims abstract description 123
- 239000012790 adhesive layer Substances 0.000 claims abstract description 115
- 229920001400 block copolymer Polymers 0.000 claims description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 54
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- -1 2-ethylhexyl Chemical group 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229920000428 triblock copolymer Polymers 0.000 claims description 11
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000011496 polyurethane foam Substances 0.000 claims description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000002076 thermal analysis method Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 36
- 230000001070 adhesive effect Effects 0.000 abstract description 35
- 230000037303 wrinkles Effects 0.000 abstract description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- 239000003431 cross linking reagent Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
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- 238000000034 method Methods 0.000 description 13
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
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- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Abstract
本發明之目的在於，提供一種具有優異之應力緩和性及耐衝擊性、兩黏著面之二次加工（rework）性優異、且可抑制皺褶或折痕之產生並容易地捲繞成卷狀之雙面黏著帶。 本發明係一種雙面黏著帶，其具有發泡體基材、且於上述發泡體基材之雙面分別具有第1黏著劑層及第2黏著劑層，且於上述發泡體基材與上述第1黏著劑層之間、及上述發泡體基材與上述第2黏著劑層之間分別具有拉伸斷裂點應力為4 MPa以上之第1樹脂層及第2樹脂層，上述第1樹脂層及第2樹脂層之至少一者之拉伸彈性模數為50 MPa以下。An object of the present invention is to provide a product that has excellent stress relaxation properties and impact resistance, is excellent in reworkability of both adhesive surfaces, can suppress the occurrence of wrinkles or creases, and can be easily wound into a roll. Double-sided adhesive tape. The present invention is a double-sided adhesive tape, which has a foam base material, and has a first adhesive layer and a second adhesive layer on both sides of the foam base material. Between the above-mentioned first adhesive layer and between the above-mentioned foam base material and the above-mentioned second adhesive layer, there are respectively a first resin layer and a second resin layer with a tensile breaking point stress of 4 MPa or more. The tensile elastic modulus of at least one of the first resin layer and the second resin layer is 50 MPa or less.
Description
本發明係關於一種具有優異之應力緩和性及耐衝擊性、兩黏著面之二次加工（rework）性優異、且可抑制皺褶或折痕之產生並容易地捲繞成卷狀之雙面黏著帶。The present invention relates to a double-sided adhesive tape that has excellent stress relaxation and impact resistance, excellent reworkability on both adhesive surfaces, suppresses the occurrence of wrinkles or creases, and can be easily rolled into a roll. Adhesive tape.
於行動電話、行動資訊終端（Personal Digital Assistants，PDA）等可攜式電子機器中，雙面黏著帶用於組裝（例如，專利文獻1、2）。又，雙面黏著帶亦用於將車載用面板等車載用電子機器零件固定於車輛本體之用途。 先前技術文獻 專利文獻In portable electronic devices such as mobile phones and mobile information terminals (Personal Digital Assistants, PDAs), double-sided adhesive tapes are used for assembly (for example, Patent Documents 1 and 2). In addition, double-sided adhesive tapes are also used to fix vehicle-mounted electronic equipment parts such as vehicle-mounted panels to the vehicle body. Prior technical literature patent documents
專利文獻1：日本特開2009-242541號公報 專利文獻2：日本特開2009-258274號公報Patent Document 1: Japanese Patent Application Publication No. 2009-242541 Patent Document 2: Japanese Patent Application Publication No. 2009-258274
[發明所欲解決之課題][Problem to be solved by the invention]
作為用於固定可攜式電子機器零件、車載用電子機器零件等之雙面黏著帶，要求較高之黏著力。進而，近年來，可攜式電子機器、車載用電子機器等有隨著高功能化而形狀更加複雜化之傾向，因此，存在將雙面黏著帶貼附於階差、角、非平面部等而使用之情況。於此種情形時，由於將雙面黏著帶於變形之狀態下固定，故欲恢復至原形狀之力、即回覆力或反彈力發揮作用，從而存在雙面黏著帶隨著時間經過而剝離之情況。特別是於將零件於變形之狀態下固定之情形時，由於零件本身欲恢復至原形狀，故回覆力或反彈力施加於雙面黏著帶，從而存在固定不充分、或雙面黏著帶剝離之情況。為了防止由此種回覆力或反彈力所導致之剝離，對雙面黏著帶要求優異之應力緩和性。又，亦存在對雙面黏著帶要求耐衝擊性之情況。As a double-sided adhesive tape used to fix portable electronic equipment parts, vehicle-mounted electronic equipment parts, etc., high adhesion is required. Furthermore, in recent years, portable electronic devices, vehicle-mounted electronic devices, etc. tend to have more complex shapes as they become more functional. Therefore, double-sided adhesive tapes are attached to steps, corners, non-planar parts, etc. And the situation of use. In this case, since the double-sided adhesive tape is fixed in a deformed state, the force to return to the original shape, that is, the restoring force or rebound force, acts, and the double-sided adhesive tape may peel off over time. condition. Especially when a part is fixed in a deformed state, since the part itself wants to return to its original shape, a restoring force or rebound force is exerted on the double-sided adhesive tape, resulting in insufficient fixation or peeling of the double-sided adhesive tape. condition. In order to prevent peeling due to such restoring force or rebound force, double-sided adhesive tapes are required to have excellent stress relaxation properties. In addition, there are cases where the double-sided adhesive tape is required to have impact resistance.
作為具有優異之應力緩和性且耐衝擊性亦優異之雙面黏著帶，已知有使用發泡體基材之雙面黏著帶。然而，習知之使用發泡體基材之雙面黏著帶於用於暫時固定之用途之情形時、或由於某種狀況而貼合後欲剝離之情形時，存在剝離時發泡體基材破裂、殘渣殘留於被黏著體之情況，存在二次加工性較差之情況。特別是對於雙面黏著帶，要求兩黏著面之二次加工性。 又，雙面黏著帶通常於捲繞成卷狀之狀態下提供，自該卷狀體捲出而使用。此時，雙面黏著帶若不充分柔軟，則存在捲繞成卷狀時之操作性降低、或捲繞時產生皺褶或折痕之情況。As a double-sided adhesive tape having excellent stress relaxation properties and excellent impact resistance, a double-sided adhesive tape using a foam base material is known. However, when the conventional double-sided adhesive tape using a foam base material is used for temporary fixation, or when it is peeled off after being attached due to certain circumstances, the foam base material may break during peeling. . If residue remains on the adherend, secondary processability may be poor. Especially for double-sided adhesive tapes, secondary processability of both adhesive surfaces is required. In addition, the double-sided adhesive tape is usually provided in a state of being wound into a roll, and is rolled out from the roll before use. At this time, if the double-sided adhesive tape is not sufficiently soft, the operability when wound into a roll may be reduced, or wrinkles or creases may occur during winding.
本發明之目的在於，提供一種具有優異之應力緩和性及耐衝擊性、兩黏著面之二次加工性優異、且可抑制皺褶或折痕之產生並容易地捲繞成卷狀之雙面黏著帶。 [解決課題之技術手段]An object of the present invention is to provide a double-sided adhesive that has excellent stress relaxation and impact resistance, excellent secondary processability on both adhesive surfaces, suppresses the occurrence of wrinkles or creases, and can be easily rolled into a roll. Adhesive tape. [Technical means to solve the problem]
本發明係一種雙面黏著帶，其係具有發泡體基材、且於上述發泡體基材之雙面分別具有第1黏著劑層及第2黏著劑層者，且於上述發泡體基材與上述第1黏著劑層之間、及上述發泡體基材與上述第2黏著劑層之間分別具有拉伸斷裂點應力為4 MPa以上之第1樹脂層及第2樹脂層，上述第1樹脂層及第2樹脂層之至少一者之拉伸彈性模數為50 MPa以下。 以下對本發明進行詳述。The present invention is a double-sided adhesive tape, which has a foam base material, and has a first adhesive layer and a second adhesive layer on both sides of the foam base material, and has a first adhesive layer and a second adhesive layer on both sides of the foam base material. Between the base material and the above-mentioned first adhesive layer, and between the above-mentioned foam base material and the above-mentioned second adhesive layer, there are respectively a first resin layer and a second resin layer with a tensile breaking point stress of 4 MPa or more, The tensile elastic modulus of at least one of the first resin layer and the second resin layer is 50 MPa or less. The present invention will be described in detail below.
本發明人等在具有發泡體基材、且於該發泡體基材之雙面分別具有第1黏著劑層及第2黏著劑層之雙面黏著帶中，於發泡體基材與第1黏著劑層之間、及發泡體基材與第2黏著劑層之間分別配置拉伸斷裂點應力為一定程度以上之第1樹脂層及第2樹脂層。本發明人等發現，藉由配置此種第1樹脂層及第2樹脂層，可採用能夠發揮優異之應力緩和性及耐衝擊性之發泡體基材，並且使兩黏著面發揮優異之二次加工性。本發明人等進一步進行潛心研究，結果發現藉由將第1樹脂層及第2樹脂層之至少一者之拉伸彈性模數設為一定程度以下，可確保兩黏著面之二次加工性，並且抑制皺褶或折痕之產生並容易地捲繞成卷狀，從而完成了本發明。The present inventors developed a double-sided adhesive tape having a foam base material and a first adhesive layer and a second adhesive layer on both sides of the foam base material. A first resin layer and a second resin layer each having a tensile breaking point stress exceeding a certain level are disposed between the first adhesive layers and between the foam base material and the second adhesive layer. The present inventors discovered that by arranging such a first resin layer and a second resin layer, a foam base material that can exhibit excellent stress relaxation properties and impact resistance can be used, and both adhesive surfaces can exhibit excellent performance. Processability. The present inventors conducted further intensive research and found that by setting the tensile elastic modulus of at least one of the first resin layer and the second resin layer below a certain level, the secondary processability of both adhesive surfaces can be ensured. Furthermore, the present invention was completed by suppressing the occurrence of wrinkles or creases and easily winding it into a roll shape.
圖1示出表示本發明之一實施態樣之雙面黏著帶之一例之示意圖。圖1之本發明之一實施態樣之雙面黏著帶1於發泡體基材2之雙面具有第1黏著劑層31及第2黏著劑層32。而且，於發泡體基材2與第1黏著劑層31之間配置有第1樹脂層41，於發泡體基材2與第2黏著劑層32之間配置有第2樹脂層42。FIG. 1 is a schematic diagram showing an example of a double-sided adhesive tape according to an embodiment of the present invention. The double-sided adhesive tape 1 of one embodiment of the present invention in Figure 1 has a first adhesive layer 31 and a second adhesive layer 32 on both sides of the foam base material 2. Furthermore, the first resin layer 41 is arranged between the foam base material 2 and the first adhesive layer 31 , and the second resin layer 42 is arranged between the foam base material 2 and the second adhesive layer 32 .
本發明之一實施態樣之雙面黏著帶具有發泡體基材、且於該發泡體基材之雙面分別具有第1黏著劑層及第2黏著劑層。 藉由使用上述發泡體基材，本發明之一實施態樣之雙面黏著帶可發揮優異之應力緩和性及耐衝擊性。上述發泡體基材可具有連續氣泡結構，亦可具有獨立氣泡結構，較佳為具有連續氣泡結構。藉由使用具有連續氣泡結構之發泡體基材，可發揮更優異之應力緩和性及耐衝擊性。上述發泡體基材可為單層構造，亦可為多層構造。A double-sided adhesive tape according to an embodiment of the present invention has a foam base material, and has a first adhesive layer and a second adhesive layer on both sides of the foam base material. By using the above-mentioned foam base material, the double-sided adhesive tape according to one embodiment of the present invention can exhibit excellent stress relaxation properties and impact resistance. The above-mentioned foam base material may have a continuous cell structure or an independent cell structure, and preferably has a continuous cell structure. By using a foam base material with a continuous cell structure, better stress relaxation and impact resistance can be exerted. The above-mentioned foam base material may have a single-layer structure or a multi-layer structure.
上述發泡體基材並未特別限定，例如，可列舉聚胺酯發泡體、聚烯烴發泡體、橡膠系樹脂發泡體、丙烯酸發泡體等。其中，就易於形成連續氣泡結構、可發揮優異之應力緩和性及耐衝擊性之方面而言，較佳為聚胺酯發泡體或聚烯烴發泡體。The foam base material is not particularly limited, and examples thereof include polyurethane foam, polyolefin foam, rubber-based resin foam, and acrylic foam. Among them, polyurethane foam or polyolefin foam is preferred because it is easy to form a continuous cell structure and can exhibit excellent stress relaxation properties and impact resistance.
上述發泡體基材之密度並未特別限定，較佳之下限為0.03 g/cm3 ，較佳之上限為0.8 g/cm3 。藉由將上述發泡體基材之密度設為該範圍內，可維持雙面黏著帶之強度，並且發揮優異之應力緩和性及耐衝擊性。就雙面黏著帶之強度、應力緩和性及耐衝擊性之觀點而言，上述基材之更佳之下限為0.04 g/cm3 ，更佳之上限為0.7 g/cm3 ，進而較佳之下限為0.05 g/cm3 ，進而較佳之上限為0.6 g/cm3 ，特佳之下限為0.06 g/cm3 ，特佳之上限為0.5 g/cm3 。 再者，密度可依據JIS K 6767使用電子比重計（例如，MIRAGE公司製造，「ED120T」）而測定。The density of the above-mentioned foam base material is not particularly limited, but a preferred lower limit is 0.03 g/cm 3 and a preferred upper limit is 0.8 g/cm 3 . By setting the density of the foam base material within this range, the strength of the double-sided adhesive tape can be maintained and excellent stress relaxation and impact resistance can be exhibited. From the viewpoint of the strength, stress relaxation and impact resistance of the double-sided adhesive tape, the more preferable lower limit of the above-mentioned base material is 0.04 g/cm 3 , the more preferable upper limit is 0.7 g/cm 3 , and the more preferable lower limit is 0.05 g/cm 3 , and the preferable upper limit is 0.6 g/cm 3 , the particularly preferable lower limit is 0.06 g/cm 3 , and the particularly preferable upper limit is 0.5 g/cm 3 . Furthermore, the density can be measured using an electronic hydrometer (for example, "ED120T" manufactured by MIRAGE Co., Ltd.) in accordance with JIS K 6767.
上述發泡體基材之25%壓縮強度並未特別限定，較佳之下限為1 kPa，較佳之上限為100 kPa。藉由將上述發泡體基材之25%壓縮強度設為該範圍內，可維持雙面黏著帶之強度，並且發揮優異之應力緩和性及耐衝擊性。就進一步提高雙面黏著帶之強度、應力緩和性及耐衝擊性之觀點而言，上述基材之25%壓縮強度之更佳之下限為3 kPa，更佳之上限為80 kPa，進而較佳之下限為5 kPa，進而較佳之上限為70 kPa。 再者，25%壓縮強度可藉由依據JIS K 6254進行測定而求得。The 25% compressive strength of the above-mentioned foam base material is not particularly limited, but the preferred lower limit is 1 kPa and the preferred upper limit is 100 kPa. By setting the 25% compressive strength of the foam base material within this range, the strength of the double-sided adhesive tape can be maintained while exhibiting excellent stress relaxation and impact resistance. From the perspective of further improving the strength, stress relaxation and impact resistance of the double-sided adhesive tape, the more preferable lower limit of the 25% compressive strength of the above base material is 3 kPa, the more preferable upper limit is 80 kPa, and the more preferable lower limit is 5 kPa, and a better upper limit is 70 kPa. In addition, the 25% compressive strength can be obtained by measuring according to JIS K 6254.
上述發泡體基材之剪切儲存彈性模數並未特別限定，藉由動態黏彈性裝置所測定且於基準溫度23℃合成之主曲線上之頻率1.0×10-4 ～1.0×10-5 Hz區域中之剪切儲存彈性模數之最大值較佳為1.0×105 Pa以下。上述頻率區域係與回覆力或反彈力施加於雙面黏著帶時所產生之低速剝離應力相對應之頻率。若上述頻率區域中之剪切儲存彈性模數之最大值為1.0×105 Pa以下，則回覆力或反彈力施加於雙面黏著帶時之應力藉由上述發泡體基材而緩和，不易傳遞至黏著劑層，因此，可提高雙面黏著帶之應力緩和性及耐衝擊性。 再者，剪切儲存彈性模數可將升溫速度設為5℃/min於-60℃～250℃之範圍內使用動態黏彈性測定裝置（例如，IT計測公司製造之DVA-200等）而測定。於測定剪切儲存彈性模數時，測定中為了抑制試樣之偏移，於上述基材之兩側塗佈黏著劑而進行測定。此種黏著劑並未特別限定，以塗佈於上述基材之兩側之黏著劑之厚度為上述基材之厚度之15%以下之方式調整而進行測定。藉由將黏著劑之厚度設為上述基材之厚度之15%以下，可極力排除黏著劑之影響而測定上述基材之剪切儲存彈性模數。The shear storage elastic modulus of the above-mentioned foam base material is not particularly limited. It is measured by a dynamic viscoelastic device and has a frequency of 1.0×10 -4 to 1.0×10 -5 on the main curve synthesized at a reference temperature of 23°C. The maximum value of the shear storage elastic modulus in the Hz region is preferably 1.0×10 5 Pa or less. The above-mentioned frequency range corresponds to the low-speed peeling stress generated when a restoring force or rebound force is applied to the double-sided adhesive tape. If the maximum value of the shear storage elastic modulus in the above frequency range is 1.0×10 5 Pa or less, the stress when the restoring force or rebound force is applied to the double-sided adhesive tape is relaxed by the above-mentioned foam base material, and it is not easy to It is transferred to the adhesive layer, thus improving the stress relaxation and impact resistance of the double-sided adhesive tape. Furthermore, the shear storage elastic modulus can be measured using a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Measurement Co., Ltd., etc.) in the range of -60°C to 250°C by setting the heating rate to 5°C/min. . When measuring the shear storage elastic modulus, in order to suppress the deflection of the sample during the measurement, adhesive is coated on both sides of the above-mentioned base material and measured. This adhesive is not particularly limited, and is measured so that the thickness of the adhesive applied on both sides of the base material is adjusted to be 15% or less of the thickness of the base material. By setting the thickness of the adhesive to less than 15% of the thickness of the base material, the influence of the adhesive can be eliminated while measuring the shear storage elastic modulus of the base material.
上述發泡體基材之厚度並未特別限定，較佳之下限為100 μm，較佳之上限為2900 μm。藉由將上述發泡體基材之厚度設為該範圍內，可將本發明之一實施態樣之雙面黏著帶良好地用於固定可攜式電子機器零件、車載用電子機器零件等。就可更良好地用於固定上述零件等之觀點而言，上述發泡體基材之厚度之更佳之下限為200 μm，更佳之上限為2500 μm，進而較佳之下限為250 μm，進而較佳之上限為2000 μm，特佳之下限為300 μm，特佳之上限為1500 μm。The thickness of the above-mentioned foam base material is not particularly limited, but a preferred lower limit is 100 μm and a preferred upper limit is 2900 μm. By setting the thickness of the foam base material within this range, the double-sided adhesive tape according to one embodiment of the present invention can be suitably used for fixing portable electronic device parts, vehicle-mounted electronic device parts, and the like. From the viewpoint of being more suitable for fixing the above-mentioned parts and the like, the lower limit of the thickness of the foam base material is preferably 200 μm, the upper limit is more preferably 2500 μm, the lower limit is more preferably 250 μm, and the upper limit is more preferably 250 μm. The upper limit is 2000 μm, the lower limit of the best is 300 μm, and the upper limit of the best is 1500 μm.
上述第1黏著劑層與第2黏著劑層（以下，亦將兩者統稱為「黏著劑層」）可為相同之組成，亦可分別為不同之組成。上述黏著劑層並未特別限定，例如，可列舉丙烯酸黏著劑層、橡膠系黏著劑層、胺酯黏著劑層、聚矽氧系黏著劑層等。其中，就對光、熱、水分等相對較穩定、可接著於各種被黏著體（被黏著體選擇性較低）之方面而言，較佳為含有丙烯酸共聚物之丙烯酸黏著劑層。The above-mentioned first adhesive layer and second adhesive layer (hereinafter, both are also collectively referred to as "adhesive layers") may have the same composition, or may have different compositions. The adhesive layer is not particularly limited, and examples thereof include an acrylic adhesive layer, a rubber adhesive layer, a urethane adhesive layer, a polysiloxane adhesive layer, and the like. Among them, an acrylic adhesive layer containing an acrylic copolymer is preferred because it is relatively stable against light, heat, moisture, etc., and can be adhered to various adherends (the selectivity of the adherends is low).
構成上述丙烯酸黏著劑層之丙烯酸共聚物就由於初期之觸黏性提高，故低溫時之貼附容易性變得良好之觀點而言，較佳為使包含丙烯酸丁酯及/或丙烯酸2-乙基己酯之單體混合物共聚而獲得。更佳為使包含丙烯酸丁酯及丙烯酸2-乙基己酯之單體混合物共聚而獲得。 上述丙烯酸丁酯於全部單體混合物中所占之含量之較佳之下限為40重量%，較佳之上限為80重量%。藉由將上述丙烯酸丁酯之含量設為該範圍內，可兼顧較高之黏著力與觸黏性。 上述丙烯酸2-乙基己酯於全部單體混合物中所占之含量之較佳之下限為10重量%，較佳之上限為100重量%，更佳之下限為30重量%，更佳之上限為80重量%，進而較佳之下限為50重量%，進而較佳之上限為60重量%。藉由將上述丙烯酸2-乙基己酯之含量設為該範圍內，可發揮較高之黏著力。The acrylic copolymer constituting the above-mentioned acrylic adhesive layer preferably contains butyl acrylate and/or 2-ethyl acrylate from the viewpoint of improving the ease of adhesion at low temperatures due to improved initial tackiness. Obtained by copolymerization of monomer mixture of hexyl hexyl ester. More preferably, it is obtained by copolymerizing a monomer mixture including butyl acrylate and 2-ethylhexyl acrylate. The preferred lower limit of the content of the above-mentioned butyl acrylate in the entire monomer mixture is 40% by weight, and the preferred upper limit is 80% by weight. By setting the content of the above-mentioned butyl acrylate within this range, both higher adhesive force and tackiness can be achieved. The preferred lower limit of the content of the above-mentioned 2-ethylhexyl acrylate in the entire monomer mixture is 10% by weight, the preferred upper limit is 100% by weight, the preferred lower limit is 30% by weight, and the preferred upper limit is 80% by weight. , a further preferable lower limit is 50% by weight, and a further preferable upper limit is 60% by weight. By setting the content of the above-mentioned 2-ethylhexyl acrylate within this range, higher adhesive force can be exerted.
上述單體混合物可視需要包含除丙烯酸丁酯及丙烯酸2-乙基己酯以外之可共聚之其他聚合性單體。作為上述可共聚之其他聚合性單體，例如，可列舉烷基之碳數為1～3之(甲基)丙烯酸烷基酯、烷基之碳數為13～18之(甲基)丙烯酸烷基酯、官能性單體等。 作為上述烷基之碳數為1～3之(甲基)丙烯酸烷基酯，例如，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯等。作為上述烷基之碳數為13～18之(甲基)丙烯酸烷基酯，例如，可列舉甲基丙烯酸十三烷基酯、(甲基)丙烯酸硬脂酯等。作為上述官能性單體，例如，可列舉(甲基)丙烯酸羥烷基酯、甘油二甲基丙烯酸酯、(甲基)丙烯酸縮水甘油酯、異氰酸2-甲基丙烯醯氧基乙酯、(甲基)丙烯酸、伊康酸、馬來酸酐、丁烯酸、馬來酸、富馬酸等。The above monomer mixture may optionally contain other copolymerizable polymerizable monomers other than butyl acrylate and 2-ethylhexyl acrylate. Examples of other copolymerizable polymerizable monomers include alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms, and alkyl (meth)acrylate having an alkyl group having 13 to 18 carbon atoms. esters, functional monomers, etc. Examples of the alkyl (meth)acrylate in which the alkyl group has 1 to 3 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, etc. Examples of the (meth)acrylic acid alkyl ester in which the alkyl group has 13 to 18 carbon atoms include tridecyl methacrylate, stearyl (meth)acrylate, and the like. Examples of the functional monomer include hydroxyalkyl (meth)acrylate, glyceryl dimethacrylate, glycidyl (meth)acrylate, and 2-methacryloyloxyethyl isocyanate. , (meth)acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid, fumaric acid, etc.
為了使上述單體混合物共聚而獲得上述丙烯酸共聚物，可使上述單體混合物於聚合起始劑之存在下發生自由基反應。作為使上述單體混合物發生自由基反應之方法、即聚合方法，可使用先前公知之方法，例如，可列舉溶液聚合（沸點聚合或恆溫聚合）、乳化聚合、懸濁聚合、塊狀聚合等。In order to copolymerize the above-mentioned monomer mixture to obtain the above-mentioned acrylic acid copolymer, the above-mentioned monomer mixture may be subjected to a free radical reaction in the presence of a polymerization initiator. As a method for radically reacting the monomer mixture, that is, a polymerization method, a conventionally known method can be used, and examples include solution polymerization (boiling point polymerization or isothermal polymerization), emulsion polymerization, suspension polymerization, block polymerization, and the like.
上述丙烯酸共聚物之重量平均分子量（Mw）之較佳之下限為40萬，較佳之上限為150萬。藉由將上述丙烯酸共聚物之重量平均分子量設為該範圍內，可發揮較高之黏著力。就黏著力進一步提高之觀點而言，上述重量平均分子量之更佳之下限為50萬，更佳之上限為140萬。 再者，重量平均分子量（Mw）係指利用GPC（Gel Permeation Chromatography：凝膠滲透層析法）之標準聚苯乙烯換算之重量平均分子量。The preferred lower limit of the weight average molecular weight (Mw) of the acrylic copolymer is 400,000, and the preferred upper limit is 1.5 million. By setting the weight average molecular weight of the acrylic copolymer within this range, higher adhesive force can be exerted. From the viewpoint of further improving the adhesive force, a more preferable lower limit of the weight average molecular weight is 500,000, and a more preferable upper limit is 1.4 million. In addition, the weight average molecular weight (Mw) refers to the weight average molecular weight converted to standard polystyrene using GPC (Gel Permeation Chromatography).
上述丙烯酸共聚物之重量平均分子量（Mw）相對於數量平均分子量（Mn）之比（Mw/Mn）之較佳之上限為10.0。若Mw/Mn為10.0以下，則抑制低分子成分之比率，抑制上述黏著劑層於高溫下軟化而導致塊體強度降低、接著強度降低。就相同之觀點而言，Mw/Mn之更佳之上限為5.0，進而較佳之上限為3.0。A preferable upper limit of the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic copolymer is 10.0. If Mw/Mn is 10.0 or less, the ratio of low molecular components is suppressed, and the adhesive layer is suppressed from softening at high temperatures, resulting in a decrease in bulk strength and a decrease in bonding strength. From the same point of view, a more preferable upper limit of Mw/Mn is 5.0, and a further preferable upper limit is 3.0.
上述黏著劑層可含有黏著賦予樹脂。 作為上述黏著賦予樹脂，例如，可列舉松香酯系樹脂、氫化松香系樹脂、萜烯系樹脂、萜酚系樹脂、薰草哢-茚系樹脂、脂環族飽和烴系樹脂、C5系石油樹脂、C9系石油樹脂、C5-C9共聚系石油樹脂等。該等黏著賦予樹脂可單獨使用，亦可併用2種以上。The adhesive layer may contain an adhesive imparting resin. Examples of the tackifier-imparting resin include rosin ester resin, hydrogenated rosin resin, terpene resin, terpenol resin, lavenderine-indene resin, alicyclic saturated hydrocarbon resin, and C5 petroleum resin. , C9 series petroleum resin, C5-C9 copolymer series petroleum resin, etc. These adhesion-imparting resins may be used alone, or two or more types may be used in combination.
上述黏著賦予樹脂之含量並未特別限定，相對於作為上述黏著劑層之主成分之樹脂（例如，丙烯酸共聚物）100重量份，較佳之下限為10重量份，較佳之上限為60重量份。若上述黏著賦予樹脂之含量為10重量份以上，則可抑制上述黏著劑層之黏著力之降低。若上述黏著賦予樹脂之含量為60重量份以下，則可抑制因上述黏著劑層變硬所導致之黏著力或觸黏性之降低。The content of the adhesion-imparting resin is not particularly limited, but a preferred lower limit is 10 parts by weight and a preferred upper limit is 60 parts by weight based on 100 parts by weight of the resin (for example, acrylic copolymer) that is the main component of the adhesive layer. If the content of the adhesive imparting resin is 10 parts by weight or more, the reduction in the adhesive force of the adhesive layer can be suppressed. If the content of the above-mentioned adhesive imparting resin is 60 parts by weight or less, the decrease in adhesive force or tack caused by the hardening of the above-mentioned adhesive layer can be suppressed.
上述黏著劑層較佳為藉由添加交聯劑而於構成上述黏著劑層之樹脂（例如，上述丙烯酸共聚物、上述黏著賦予樹脂等）之主鏈間形成有交聯結構。上述交聯劑並未特別限定，例如，可列舉異氰酸酯系交聯劑、氮丙啶系交聯劑、環氧系交聯劑、金屬螯合物型交聯劑等。其中，較佳為異氰酸酯系交聯劑。藉由將異氰酸酯系交聯劑添加於上述黏著劑層中，異氰酸酯系交聯劑之異氰酸基與構成上述黏著劑層之樹脂（例如，上述丙烯酸共聚物、上述黏著賦予樹脂等）中之醇性羥基進行反應，上述黏著劑層之交聯變得鬆散。因此，上述黏著劑層可分散斷續施加之剝離應力，雙面黏著帶之黏著力進一步提高。 上述交聯劑之添加量相對於作為上述黏著劑層之主成分之樹脂（例如，上述丙烯酸共聚物）100重量份，較佳為0.01～10重量份，更佳為0.1～7重量份。The adhesive layer preferably has a cross-linked structure formed between the main chains of the resin constituting the adhesive layer (for example, the acrylic copolymer, the tackifying resin, etc.) by adding a cross-linking agent. The cross-linking agent is not particularly limited, and examples thereof include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-type cross-linking agents, and the like. Among them, an isocyanate cross-linking agent is preferred. By adding an isocyanate cross-linking agent to the adhesive layer, the isocyanate group of the isocyanate cross-linking agent and the resin constituting the adhesive layer (for example, the acrylic copolymer, the adhesive resin, etc.) The alcoholic hydroxyl groups react and the cross-linking of the adhesive layer becomes loose. Therefore, the above-mentioned adhesive layer can disperse the peeling stress applied intermittently, and the adhesion force of the double-sided adhesive tape is further improved. The amount of the cross-linking agent added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 7 parts by weight relative to 100 parts by weight of the resin (for example, the acrylic copolymer) as the main component of the adhesive layer.
上述黏著劑層之交聯度就抑制施加有較大之剪切方向之負荷之情形時之自被黏著體之剝離的觀點而言，較佳為5～70重量%，更佳為10～60重量%，特佳為15～50重量%。再者，黏著劑層之交聯度係採集黏著劑層W1（g），將該黏著劑層於乙酸乙酯中於23℃浸漬24小時，藉由200目之金屬絲網過濾不溶解分，對金屬絲網上之殘渣進行真空乾燥，測定乾燥殘渣之重量W2（g），並根據下述式而算出。 交聯度（重量%）＝100×W2/W1The cross-linking degree of the above-mentioned adhesive layer is preferably 5 to 70% by weight, more preferably 10 to 60, from the viewpoint of suppressing peeling from the adherend when a large load in the shear direction is applied. % by weight, preferably 15 to 50% by weight. Furthermore, the cross-linking degree of the adhesive layer is obtained by collecting the adhesive layer W1 (g), immersing the adhesive layer in ethyl acetate at 23°C for 24 hours, and filtering the insoluble matter through a 200-mesh wire mesh. The residue on the wire mesh is vacuum-dried, and the weight W2 (g) of the dried residue is measured and calculated according to the following formula. Cross-linking degree (weight%) = 100×W2/W1
上述黏著劑層可以提高黏著力為目的而含有矽烷偶合劑。上述矽烷偶合劑並未特別限定，例如，可列舉環氧矽烷類、丙烯醯基矽烷類、甲基丙烯醯基矽烷類、胺基矽烷類、異氰酸酯矽烷類等。The above-mentioned adhesive layer may contain a silane coupling agent for the purpose of improving adhesion. The silane coupling agent is not particularly limited, and examples thereof include epoxy silanes, acrylyl silanes, methacrylyl silanes, amino silanes, isocyanate silanes, and the like.
上述黏著劑層可以賦予遮光性為目的而含有著色材。上述著色材並未特別限定，例如，可列舉碳黑、苯胺黑、氧化鈦等。其中，就價格相對較低且化學上較穩定之方面而言，較佳為碳黑。 上述黏著劑層可視需要含有無機微粒子、導電微粒子、抗氧化劑、發泡劑、有機填充劑、無機填充劑等先前公知之微粒子及添加劑。The adhesive layer may contain a coloring material for the purpose of imparting light-shielding properties. The coloring material is not particularly limited, and examples thereof include carbon black, aniline black, titanium oxide, and the like. Among them, carbon black is preferred in terms of its relatively low price and chemical stability. The above-mentioned adhesive layer may optionally contain previously known microparticles and additives such as inorganic microparticles, conductive microparticles, antioxidants, foaming agents, organic fillers, and inorganic fillers.
上述黏著劑層之厚度並未特別限定，單面之黏著劑層之厚度之較佳之下限為0.01 mm，較佳之上限為0.1 mm。藉由將上述黏著劑層之厚度設為該範圍內，可將本發明之一實施態樣之雙面黏著帶良好地用於固定可攜式電子機器零件、車載用電子機器零件等。就可更良好地用於固定上述零件等之觀點而言，上述黏著劑層之厚度之更佳之下限為0.015 mm，更佳之上限為0.09 mm。The thickness of the above-mentioned adhesive layer is not particularly limited. The preferred lower limit of the thickness of the adhesive layer on one side is 0.01 mm, and the preferred upper limit is 0.1 mm. By setting the thickness of the adhesive layer within this range, the double-sided adhesive tape according to one embodiment of the present invention can be used well for fixing portable electronic device parts, vehicle-mounted electronic device parts, and the like. From the viewpoint of better fixing of the above-mentioned parts and the like, the lower limit of the thickness of the adhesive layer is preferably 0.015 mm, and the upper limit is preferably 0.09 mm.
本發明之一實施態樣之雙面黏著帶於上述發泡體基材與第1黏著劑層之間、及上述發泡體基材與第2黏著劑層之間分別具有第1樹脂層及第2樹脂層（以下，亦將兩者統稱為「樹脂層」）。即，本發明之一實施態樣之雙面黏著帶於上述發泡體基材與第1黏著劑層之間具有第1樹脂層，且於上述發泡體基材與第2黏著劑層之間具有第2樹脂層。藉由具有上述樹脂層，本發明之一實施態樣之雙面黏著帶可採用能夠發揮優異之應力緩和性及耐衝擊性之上述發泡體基材，並且於剝離時不使上述發泡體基材破裂、或不於被黏著體上殘留殘渣而剝離，可使兩黏著面發揮優異之二次加工性。進而，藉由將第1樹脂層及第2樹脂層之至少一者之拉伸彈性模數設定為一定程度以下，可確保兩黏著面之二次加工性，並且抑制皺褶或折痕之產生並容易地捲繞成卷狀。The double-sided adhesive tape according to one embodiment of the present invention has a first resin layer and a first resin layer between the foam base material and the first adhesive layer, and between the foam base material and the second adhesive layer respectively. The second resin layer (hereinafter, both are also collectively referred to as the "resin layer"). That is, the double-sided adhesive tape according to one embodiment of the present invention has a first resin layer between the above-mentioned foam base material and the first adhesive layer, and between the above-mentioned foam base material and the second adhesive layer There is a second resin layer between them. By having the above-mentioned resin layer, the double-sided adhesive tape according to one embodiment of the present invention can use the above-mentioned foam base material that can exhibit excellent stress relaxation properties and impact resistance, and the above-mentioned foam can be peeled off without When the base material is cracked or peeled off without leaving any residue on the adherend, the two adhesive surfaces can exhibit excellent secondary processability. Furthermore, by setting the tensile elastic modulus of at least one of the first resin layer and the second resin layer below a certain level, the secondary processability of both adhesive surfaces can be ensured and the occurrence of wrinkles or creases can be suppressed. and easily rolled into rolls.
上述樹脂層之拉伸斷裂點應力為4 MPa以上。即，本發明之一實施態樣之雙面黏著帶於上述發泡體基材與第1黏著劑層之間具有拉伸斷裂點應力為4 MPa以上之第1樹脂層，且於上述發泡體基材與第2黏著劑層之間具有拉伸斷裂點應力為4 MPa以上之第2樹脂層。藉由使用拉伸斷裂點應力為4 MPa以上之樹脂層，可發揮優異之二次加工性。就進一步提高二次加工性之觀點而言，上述樹脂層之拉伸斷裂點應力較佳為5 MPa以上，更佳為11.5 MPa以上，進而較佳為15 MPa以上。上述樹脂層之拉伸斷裂點應力之上限並未特別限定，實質上200 MPa左右為上限。The tensile breaking point stress of the above-mentioned resin layer is above 4 MPa. That is, the double-sided adhesive tape according to one embodiment of the present invention has a first resin layer with a tensile breaking point stress of 4 MPa or more between the above-mentioned foam base material and the first adhesive layer, and between the above-mentioned foamed There is a second resin layer with a tensile breaking point stress of more than 4 MPa between the base material and the second adhesive layer. By using a resin layer with a tensile breaking point stress of 4 MPa or more, excellent secondary processability can be achieved. From the viewpoint of further improving the secondary processability, the tensile breaking point stress of the resin layer is preferably 5 MPa or more, more preferably 11.5 MPa or more, and further preferably 15 MPa or more. The upper limit of the tensile breaking point stress of the above-mentioned resin layer is not particularly limited, but is essentially about 200 MPa.
上述第1樹脂層及第2樹脂層之至少一者之拉伸彈性模數為50 MPa以下。藉由將上述第1樹脂層及第2樹脂層之至少一者設為拉伸彈性模數為50 MPa以下之柔軟之樹脂層，可確保雙面黏著帶整體之柔軟性而容易將雙面黏著帶捲繞成卷狀，操作性明顯提高，捲繞時不會產生皺褶或折痕。 再者，上述第1樹脂層及第2樹脂層之兩者之拉伸彈性模數可為50 MPa以下，亦可僅一者之拉伸彈性模數為50 MPa以下，另一者之拉伸彈性模數超過50 MPa。於上述第1樹脂層及第2樹脂層之兩者之拉伸彈性模數為50 MPa以下之情形時，雙面黏著帶之柔軟性特別優異。 於上述第1樹脂層及第2樹脂層中僅一者之拉伸彈性模數為50 MPa以下且另一者之拉伸彈性模數超過50 MPa之情形時，雙面黏著帶具有適度之硬度，因此，操作變得容易，例如容易使用刀進行切割。於該情形時，拉伸彈性模數超過50 MPa之另一樹脂層之拉伸彈性模數較佳為500 MPa以上，更佳為1000 MPa以上，進而較佳為1500 MPa以上。 上述拉伸彈性模數之下限並未特別限定，較佳為10 MPa以上，更佳為20 MPa以上。The tensile elastic modulus of at least one of the first resin layer and the second resin layer is 50 MPa or less. By making at least one of the first resin layer and the second resin layer a soft resin layer with a tensile elastic modulus of 50 MPa or less, the overall flexibility of the double-sided adhesive tape can be ensured and the double-sided adhesive tape can be easily adhered. The tape is wound into a roll shape, which significantly improves operability and does not produce wrinkles or creases during winding. Furthermore, the tensile elastic modulus of both the first resin layer and the second resin layer may be 50 MPa or less, or the tensile elastic modulus of only one may be 50 MPa or less, and the tensile elastic modulus of the other may be 50 MPa or less. The elastic modulus exceeds 50 MPa. When the tensile elastic modulus of both the first resin layer and the second resin layer is 50 MPa or less, the double-sided adhesive tape has particularly excellent flexibility. When the tensile elastic modulus of only one of the first resin layer and the second resin layer is 50 MPa or less and the tensile elastic modulus of the other exceeds 50 MPa, the double-sided adhesive tape has moderate hardness. , therefore, the operation becomes easy, such as cutting with a knife. In this case, the tensile elastic modulus of the other resin layer having a tensile elastic modulus exceeding 50 MPa is preferably 500 MPa or more, more preferably 1000 MPa or more, and further preferably 1500 MPa or more. The lower limit of the tensile elastic modulus is not particularly limited, but is preferably 10 MPa or more, more preferably 20 MPa or more.
上述拉伸彈性模數為50 MPa以下之第1樹脂層及第2樹脂層之至少一者（以下，亦稱為「拉伸彈性模數為50 MPa以下之樹脂層」）之拉伸斷裂點伸長率較佳為400%以上。藉由使上述拉伸彈性模數為50 MPa以下之樹脂層之拉伸斷裂點伸長率為400%以上，可發揮更優異之二次加工性。就進一步提高二次加工性之觀點而言，上述拉伸彈性模數為50 MPa以下之樹脂層之拉伸斷裂點伸長率較佳為450%以上，更佳為500%以上。 上述拉伸彈性模數為50 MPa以下之樹脂層之拉伸斷裂點伸長率之上限並未特別限定，實質上1500%左右為上限。The tensile breaking point of at least one of the first resin layer and the second resin layer with a tensile elastic modulus of 50 MPa or less (hereinafter, also referred to as the "resin layer with a tensile elastic modulus of 50 MPa or less") The elongation is preferably 400% or more. By setting the tensile breaking point elongation of the resin layer having a tensile elastic modulus of 50 MPa or less to 400% or more, more excellent secondary processability can be achieved. From the viewpoint of further improving the secondary processability, the tensile breaking point elongation of the resin layer having a tensile elastic modulus of 50 MPa or less is preferably 450% or more, more preferably 500% or more. The upper limit of the tensile breaking point elongation of the resin layer whose tensile elastic modulus is 50 MPa or less is not particularly limited, but is essentially about 1500%.
再者，於本說明書中，拉伸斷裂點應力、拉伸斷裂點伸長率及拉伸彈性模數意指樹脂層之機械特性，可藉由依據JIS K 7161之方法而測定。 具體而言，例如使用高分子計器公司製造之衝壓刀「拉伸1號型啞鈴狀」等於啞鈴上衝壓上述樹脂層，而製作試片。使用例如島津製作所公司製造之「Autograph AGS-X」等以拉伸速度100 mm/min對所得之試片進行測定，使試片斷裂。由試片斷裂時之每單位面積之斷裂強度算出拉伸斷裂應力。由試片斷裂時之伸長率，以「（斷裂時夾具間距離/初期夾具間距離）×100」算出拉伸斷裂點伸長率。由1～3%之應變間之拉伸強度之斜率算出拉伸彈性模數。In addition, in this specification, the tensile breaking point stress, the tensile breaking point elongation and the tensile elastic modulus mean the mechanical properties of the resin layer, and can be measured by the method according to JIS K 7161. Specifically, for example, the above-mentioned resin layer is punched on a dumbbell using a "stretch No. 1 dumbbell-shaped" punching knife manufactured by Polymer Instruments Co., Ltd., and a test piece is produced. The obtained test piece is measured using, for example, "Autograph AGS-X" manufactured by Shimadzu Corporation, at a tensile speed of 100 mm/min, and the test piece is broken. The tensile breaking stress is calculated from the breaking strength per unit area when the test piece breaks. From the elongation at break of the test piece, calculate the elongation at the tensile breaking point as "(distance between clamps at break/distance between initial clamps) × 100". The tensile elastic modulus is calculated from the slope of the tensile strength between 1 and 3% strain.
構成上述樹脂層之樹脂並未特別限定，例如，可列舉聚對苯二甲酸乙二酯等聚酯系樹脂、丙烯酸系樹脂、聚乙烯系樹脂、聚丙烯系樹脂、聚氯乙烯、環氧樹脂、聚矽氧樹脂、酚樹脂、聚醯亞胺、聚酯系樹脂、聚碳酸酯等。其中，就黏著帶之柔軟性優異之方面而言，較佳為丙烯酸系樹脂、聚乙烯系樹脂、聚丙烯系樹脂、聚酯系樹脂。聚酯系樹脂之中，較佳為聚對苯二甲酸乙二酯。The resin constituting the resin layer is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate, acrylic resins, polyethylene resins, polypropylene resins, polyvinyl chloride, and epoxy resins. , polysilicone resin, phenol resin, polyimide, polyester resin, polycarbonate, etc. Among these, in terms of excellent flexibility of the adhesive tape, acrylic resins, polyethylene resins, polypropylene resins, and polyester resins are preferred. Among polyester-based resins, polyethylene terephthalate is preferred.
上述拉伸彈性模數為50 MPa以下之樹脂層就進一步提高應力緩和性、耐衝擊性及二次加工性之觀點而言，較佳為含有熱塑性彈性體。 上述熱塑性彈性體可為苯乙烯系（共）聚合物、烯烴系（共）聚合物、氯乙烯系（共）聚合物、聚醚酯系三嵌段系（共）聚合物、聚酯系（共）聚合物、胺酯系（共）聚合物、醯胺系（共）聚合物或丙烯酸系（共）聚合物。其中，就可發揮作為彈性體之強度、伸長率、柔軟性、自黏著性，可發揮優異之二次加工性並且進一步提高樹脂層與發泡體基材之密接性之觀點而言，上述熱塑性彈性體較佳為丙烯酸系（共）聚合物、苯乙烯系（共）聚合物或烯烴系（共）聚合物。進而，更佳為丙烯酸系（共）聚合物或苯乙烯系（共）聚合物，進而較佳為苯乙烯系（共）聚合物。 上述拉伸彈性模數為50 MPa以下之樹脂層中之上述熱塑性彈性體之含量較佳為70重量%以上，更佳為80重量%以上，進而較佳為90重量%以上，特佳為95重量%以上，可為100重量%，通常為100重量%以下。The resin layer having a tensile elastic modulus of 50 MPa or less preferably contains a thermoplastic elastomer from the viewpoint of further improving stress relaxation, impact resistance and secondary processability. The above-mentioned thermoplastic elastomer can be a styrenic (co)polymer, an olefin (co)polymer, a vinyl chloride (co)polymer, a polyetherester triblock (co)polymer, a polyester (co)polymer Co)polymer, urethane (co)polymer, amide (co)polymer or acrylic (co)polymer. Among them, the above-mentioned thermoplastic properties can exhibit the strength, elongation, softness, and self-adhesiveness of elastomers, exhibit excellent secondary processability, and further improve the adhesion between the resin layer and the foam base material. The elastomer is preferably an acrylic (co)polymer, a styrenic (co)polymer or an olefin (co)polymer. Furthermore, an acrylic (co)polymer or a styrenic (co)polymer is more preferred, and a styrenic (co)polymer is still more preferred. The content of the thermoplastic elastomer in the resin layer with a tensile elastic modulus of 50 MPa or less is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and particularly preferably 95% by weight. More than 100% by weight, may be 100% by weight, usually less than 100% by weight.
於本發明之較佳之實施態樣中，上述拉伸彈性模數為50 MPa以下之樹脂層就進一步提高應力緩和性、耐衝擊性及二次加工性之觀點而言，較佳為含有嵌段共聚物。尤其更佳為含有具有硬鏈段及軟鏈段之嵌段共聚物。 再者，於進行該樹脂層之示差掃描熱析法（DSC）時，以23℃為分界上下分別觀察到1個以上之峰，藉此，可確認上述拉伸彈性模數為50 MPa以下之樹脂層由上述具有硬鏈段及軟鏈段之嵌段共聚物所構成。In a preferred embodiment of the present invention, the resin layer with a tensile elastic modulus of 50 MPa or less preferably contains blocks from the viewpoint of further improving stress relaxation, impact resistance and secondary processability. copolymer. Particularly preferred are block copolymers containing hard segments and soft segments. Furthermore, when differential scanning thermography (DSC) was performed on the resin layer, more than one peak was observed at the top and bottom with 23°C as the boundary. From this, it was confirmed that the above-mentioned tensile elastic modulus was 50 MPa or less. The resin layer is composed of the above-mentioned block copolymer having hard segments and soft segments.
於本發明之進而較佳之實施態樣中，上述拉伸彈性模數為50 MPa以下之樹脂層更佳為含有三嵌段共聚物。尤其進而較佳為含有具有硬鏈段及軟鏈段之三嵌段共聚物。藉由使用此種三嵌段共聚物，可發揮作為彈性體之強度、伸長率、柔軟性、自黏著性，可發揮優異之二次加工性，並且進一步提高樹脂層與發泡體基材之密接性。In a further preferred embodiment of the present invention, the resin layer having a tensile elastic modulus of 50 MPa or less preferably contains a triblock copolymer. In particular, a triblock copolymer containing a hard segment and a soft segment is more preferred. By using this triblock copolymer, the strength, elongation, softness, and self-adhesive properties of the elastomer can be exerted, and excellent secondary processability can be exerted, and the bonding between the resin layer and the foam base material can be further improved. Tightness.
進而，上述拉伸彈性模數為50 MPa以下之樹脂層就進一步提高應力緩和性、耐衝擊性及二次加工性之觀點而言，亦較佳為含有二嵌段共聚物及三嵌段共聚物，即由二嵌段共聚物與三嵌段共聚物之混合物所構成。 於本發明之較佳之實施態樣中，上述拉伸彈性模數為50 MPa以下之樹脂層中之三嵌段共聚物之含量就進一步提高應力緩和性、耐衝擊性及二次加工性之觀點而言，較佳為60重量%以上。更佳為70重量%以上，進而較佳為80重量%以上，特佳為90重量%以上，可為100重量%，通常為100重量%以下。Furthermore, the resin layer having a tensile elastic modulus of 50 MPa or less preferably contains a diblock copolymer and a triblock copolymer from the viewpoint of further improving stress relaxation, impact resistance and secondary processability. It is composed of a mixture of diblock copolymer and triblock copolymer. In a preferred embodiment of the present invention, the content of the triblock copolymer in the resin layer with a tensile elastic modulus of 50 MPa or less further improves stress relaxation, impact resistance and secondary processability. In terms of weight, it is preferably 60% by weight or more. More preferably, it is 70% by weight or more, still more preferably 80% by weight or more, particularly preferably 90% by weight or more, and may be 100% by weight, but is usually 100% by weight or less.
於上述嵌段共聚物為具有硬鏈段及軟鏈段之嵌段共聚物之情形時，硬鏈段之比率較佳為10重量%以上、50重量%以下。上述硬鏈段之比率更佳為12重量%以上、45重量%以下，進而較佳為14重量%以上、40重量%以下，特佳為35重量%以下。藉由將上述硬鏈段之比率設為該範圍內，上述樹脂層對上述發泡體基材、尤其是由聚胺酯發泡體或聚烯烴發泡體所構成之發泡體基材之密接性提高。When the block copolymer is a block copolymer having hard segments and soft segments, the ratio of the hard segments is preferably 10% by weight or more and 50% by weight or less. The ratio of the hard segments is more preferably 12% by weight or more and 45% by weight or less, further preferably 14% by weight or more and 40% by weight or less, and particularly preferably 35% by weight or less. By setting the ratio of the hard segments within this range, the adhesiveness of the resin layer to the foam base material, especially a foam base material composed of polyurethane foam or polyolefin foam, is improved. improve.
於上述嵌段共聚物為具有硬鏈段及軟鏈段之嵌段共聚物之情形時，硬鏈段之分子量較佳為5萬以上，更佳為5.3萬以上，進而較佳為5.5萬以上。上述嵌段共聚物中之硬鏈段之分子量較佳為10萬以下，更佳為7.5萬以下，進而較佳為7萬以下。若將上述硬鏈段之分子量設為該範圍內，則可發揮特別優異之二次加工性。When the above-mentioned block copolymer is a block copolymer having a hard segment and a soft segment, the molecular weight of the hard segment is preferably 50,000 or more, more preferably 53,000 or more, and still more preferably 55,000 or more. . The molecular weight of the hard segment in the above block copolymer is preferably 100,000 or less, more preferably 75,000 or less, still more preferably 70,000 or less. If the molecular weight of the hard segment is within this range, particularly excellent secondary processability can be exhibited.
於上述嵌段共聚物為具有硬鏈段及軟鏈段之嵌段共聚物之情形時，軟鏈段之比率較佳為50重量%以上、90重量%以下。更佳為55重量%以上、88重量%以下，進而較佳為60重量%以上、86重量%以下，特佳為65重量%以下。藉由將上述軟鏈段之比率設為該範圍內，上述樹脂層對上述發泡體基材、尤其是由聚胺酯發泡體或聚烯烴發泡體所構成之發泡體基材之密接性提高。When the above-mentioned block copolymer is a block copolymer having a hard segment and a soft segment, the ratio of the soft segment is preferably 50% by weight or more and 90% by weight or less. More preferably, it is 55 weight% or more and 88 weight% or less, still more preferably, it is 60 weight% or more and 86 weight% or less, and particularly preferably, it is 65 weight% or less. By setting the ratio of the soft segments within this range, the adhesiveness of the resin layer to the foam base material, especially a foam base material composed of polyurethane foam or polyolefin foam, is improved. improve.
於上述嵌段共聚物為具有硬鏈段及軟鏈段之嵌段共聚物之情形時，軟鏈段之分子量較佳為10萬以上，更佳為13萬以上，進而較佳為15萬以上。上述嵌段共聚物中之軟鏈段之分子量較佳為50萬以下，更佳為40萬以下，進而較佳為38萬以下。若將上述軟鏈段之分子量設為該範圍內，則上述拉伸彈性模數為50 MPa以下之樹脂層發揮較高之觸黏性，對上述發泡體基材、尤其是由聚胺酯發泡體或聚烯烴發泡體所構成之發泡體基材之密接性提高。When the above-mentioned block copolymer is a block copolymer having a hard segment and a soft segment, the molecular weight of the soft segment is preferably 100,000 or more, more preferably 130,000 or more, and still more preferably 150,000 or more. . The molecular weight of the soft segment in the above-mentioned block copolymer is preferably 500,000 or less, more preferably 400,000 or less, and still more preferably 380,000 or less. If the molecular weight of the above-mentioned soft segment is set within this range, the above-mentioned resin layer with a tensile elastic modulus of 50 MPa or less will exert a higher touch viscosity to the above-mentioned foam base material, especially polyurethane foam. The adhesion of the foam base material composed of polyolefin foam or polyolefin foam is improved.
於上述拉伸彈性模數為50 MPa以下之樹脂層含有上述嵌段共聚物之情形時，較佳為於利用原子力顯微鏡（AFM）觀察上述嵌段共聚物之剖面時，可觀察到球狀之相分離結構。可觀察到此種球狀之相分離結構意味著上述拉伸彈性模數為50 MPa以下之樹脂層具有微相分離結構，樹脂層可兼顧柔軟性與強度，可發揮優異之二次加工性。When the resin layer having a tensile elastic modulus of 50 MPa or less contains the block copolymer, it is preferable that when the cross-section of the block copolymer is observed with an atomic force microscope (AFM), spherical shapes can be observed. Phase separation structure. The observable spherical phase separation structure means that the above-mentioned resin layer with a tensile elastic modulus of 50 MPa or less has a micro-phase separation structure. The resin layer can have both flexibility and strength, and can exhibit excellent secondary processability.
作為上述嵌段共聚物，例如，可列舉苯乙烯系嵌段共聚物、丙烯酸系嵌段共聚物、聚醚酯系嵌段系共聚物、胺酯系嵌段共聚物、氯乙烯系嵌段共聚物、醯胺系嵌段共聚物等。 其中，就可容易地調整樹脂層之拉伸斷裂點應力、拉伸彈性模數，並發揮充分之觸黏性而容易積層於上述發泡體基材之方面而言，較佳為苯乙烯-丙烯酸系嵌段共聚物。 上述苯乙烯-丙烯酸系嵌段共聚物為苯乙烯與(甲基)丙烯酸烷基酯之嵌段共聚物。苯乙烯-丙烯酸系嵌段共聚物具有來自苯乙烯之嵌段、及來自(甲基)丙烯酸烷基酯之嵌段。再者，通常於上述苯乙烯-丙烯酸系嵌段共聚物中，來自苯乙烯之嵌段構成硬鏈段，來自(甲基)丙烯酸烷基酯之嵌段構成軟鏈段。即，較佳為包含來自苯乙烯之嵌段作為構成硬鏈段之成分且包含來自(甲基)丙烯酸烷基酯之嵌段作為構成軟鏈段之成分的苯乙烯-丙烯酸系嵌段共聚物。Examples of the block copolymer include styrene block copolymers, acrylic block copolymers, polyetherester block copolymers, urethane block copolymers, and vinyl chloride block copolymers. materials, amide block copolymers, etc. Among them, the styrene- Acrylic block copolymer. The above-mentioned styrene-acrylic block copolymer is a block copolymer of styrene and alkyl (meth)acrylate. The styrene-acrylic block copolymer has a block derived from styrene and a block derived from an alkyl (meth)acrylate. In addition, generally in the above-mentioned styrene-acrylic block copolymer, the block derived from styrene constitutes the hard segment, and the block derived from the alkyl (meth)acrylate constitutes the soft segment. That is, a styrene-acrylic block copolymer containing a block derived from styrene as a component constituting the hard segment and a block derived from an alkyl (meth)acrylate as a component constituting the soft segment is preferred. .
上述苯乙烯-丙烯酸系嵌段共聚物包含苯乙烯作為構成硬鏈段之成分。藉此，可容易地將樹脂層之拉伸斷裂點應力調整為4 MPa以上、且將拉伸彈性模數調整為50 MPa以下。 上述整個苯乙烯-丙烯酸系嵌段共聚物中的苯乙烯之比率較佳為5重量%以上，更佳為8重量%以上，進而較佳為12重量%以上。上述整個苯乙烯-丙烯酸系嵌段共聚物中的苯乙烯之比率較佳為30重量%以下，更佳為20重量%以下。 上述苯乙烯-丙烯酸系嵌段共聚物之硬鏈段中的苯乙烯之比率較佳為70重量%以上，更佳為80重量%以上。 藉由將上述苯乙烯-丙烯酸系嵌段共聚物中的苯乙烯之比率設為該範圍內，可更容易地將樹脂層之拉伸斷裂點應力調整為4 MPa以上、且將拉伸彈性模數調整為50 MPa以下。The above-mentioned styrene-acrylic block copolymer contains styrene as a component constituting the hard segment. Thereby, the tensile breaking point stress of the resin layer can be easily adjusted to 4 MPa or more, and the tensile elastic modulus can be adjusted to 50 MPa or less. The ratio of styrene in the entire styrene-acrylic block copolymer is preferably 5% by weight or more, more preferably 8% by weight or more, and still more preferably 12% by weight or more. The ratio of styrene in the entire styrene-acrylic block copolymer is preferably 30% by weight or less, more preferably 20% by weight or less. The ratio of styrene in the hard segment of the styrene-acrylic block copolymer is preferably 70% by weight or more, more preferably 80% by weight or more. By setting the styrene ratio in the styrene-acrylic block copolymer to be within this range, the tensile breaking point stress of the resin layer can be more easily adjusted to 4 MPa or more, and the tensile elastic modulus can be adjusted The number is adjusted to below 50 MPa.
上述苯乙烯-丙烯酸系嵌段共聚物亦可含有除苯乙烯以外之成分作為構成硬鏈段之成分。 作為除上述苯乙烯以外之成分，例如，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸四氫糠酯、聚丙二醇單(甲基)丙烯酸酯等(甲基)丙烯酸烷基酯。 又，例如，可使用(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸四氫糠酯等具有羥基之(甲基)丙烯酸酯。例如，可使用(甲基)丙烯酸等具有羧基之單體。例如，可使用(甲基)丙烯酸縮水甘油酯等具有縮水甘油基之單體。例如，可使用羥乙基(甲基)丙烯醯胺、異丙基(甲基)丙烯醯胺、二甲胺基丙基(甲基)丙烯醯胺等具有醯胺基之單體。可使用(甲基)丙烯腈等具有腈基之單體。 進而，例如，亦可使用乙酸乙烯酯等羧酸乙烯酯、或丙烯腈、苯乙烯等一般用於(甲基)丙烯酸共聚物之各種單體。The above-mentioned styrene-acrylic block copolymer may contain components other than styrene as components constituting the hard segment. Examples of components other than the above-mentioned styrene include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. Tert-butyl acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate , stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isocamphenyl (meth)acrylate, benzyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, ( Alkyl (meth)acrylates such as 2-phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, and polypropylene glycol mono(meth)acrylate. For example, (meth)acrylates having a hydroxyl group such as 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate can be used. For example, a monomer having a carboxyl group such as (meth)acrylic acid can be used. For example, a monomer having a glycidyl group such as glycidyl (meth)acrylate can be used. For example, monomers having a amide group, such as hydroxyethyl (meth) acrylamide, isopropyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide, can be used. Monomers having a nitrile group such as (meth)acrylonitrile can be used. Furthermore, for example, various monomers commonly used in (meth)acrylic copolymers, such as vinyl carboxylates such as vinyl acetate or acrylonitrile and styrene, can also be used.
作為除上述苯乙烯以外之成分，其中，較佳為含有具有羧基之單體。藉由含有具有羧基之單體作為構成硬鏈段之成分，上述苯乙烯-丙烯酸系嵌段共聚物可藉由交聯劑交聯。藉此，例如，藉由將交聯前之苯乙烯-丙烯酸系嵌段共聚物塗敷於上述發泡體基材上後進行交聯，可形成滿足所期望之拉伸斷裂點應力、拉伸彈性模數之樹脂層，因此，製造性提高。 於含有具有羧基之單體作為除上述苯乙烯以外之成分之情形時，硬鏈段中之具有羧基之單體之比率較佳為10重量%以上。再者，作為上述交聯劑，並未特別限定，可使用異氰酸酯系交聯劑等一般者。Among the components other than the above-mentioned styrene, it is preferable to contain a monomer having a carboxyl group. By containing a monomer having a carboxyl group as a component constituting the hard segment, the above-mentioned styrene-acrylic block copolymer can be cross-linked by a cross-linking agent. Thereby, for example, by coating the styrene-acrylic block copolymer before crosslinking on the above-mentioned foam base material and then crosslinking it, it is possible to form a layer that satisfies the desired tensile breaking point stress and tensile strength. The elastic modulus of the resin layer improves the manufacturability. When a monomer having a carboxyl group is contained as a component other than the above-mentioned styrene, the ratio of the monomer having a carboxyl group in the hard segment is preferably 10% by weight or more. In addition, the cross-linking agent is not particularly limited, and general ones such as isocyanate-based cross-linking agents can be used.
作為除上述苯乙烯以外之成分，可含有具有羥基之(甲基)丙烯酸酯。藉由包含具有羥基之(甲基)丙烯酸酯作為構成硬鏈段之成分，可提高樹脂層與發泡體基材之密接性。 於含有具有羥基之(甲基)丙烯酸酯作為除上述苯乙烯以外之成分之情形時，硬鏈段中之具有羥基之(甲基)丙烯酸酯之比率較佳為0.1重量%以上。As a component other than the above-mentioned styrene, (meth)acrylate having a hydroxyl group may be included. By including (meth)acrylate having a hydroxyl group as a component constituting the hard segment, the adhesiveness between the resin layer and the foam base material can be improved. When a (meth)acrylate having a hydroxyl group is contained as a component other than the above-mentioned styrene, the ratio of the (meth)acrylate having a hydroxyl group in the hard segment is preferably 0.1% by weight or more.
上述苯乙烯-丙烯酸系嵌段共聚物包含(甲基)丙烯酸烷基酯作為構成軟鏈段之成分。藉此，可容易地將樹脂層之拉伸斷裂點應力調整為4 MPa以上、且將拉伸彈性模數調整為50 MPa以下。The above-mentioned styrene-acrylic block copolymer contains alkyl (meth)acrylate as a component constituting the soft segment. Thereby, the tensile breaking point stress of the resin layer can be easily adjusted to 4 MPa or more, and the tensile elastic modulus can be adjusted to 50 MPa or less.
作為上述(甲基)丙烯酸烷基酯，可列舉上述作為構成硬鏈段之除苯乙烯以外之成分記載之各種(甲基)丙烯酸烷基酯。 其中，就可賦予上述拉伸彈性模數為50 MPa以下之樹脂層較高之觸黏性之方面而言，較佳為(甲基)丙烯酸正丁酯或(甲基)丙烯酸2-乙基己酯。 上述苯乙烯-丙烯酸系嵌段共聚物之軟鏈段中之(甲基)丙烯酸正丁酯或(甲基)丙烯酸2-乙基己酯之比率較佳為10重量%以上。更佳為20重量%以上，進而較佳為30重量%以上，特佳為40重量%以上，可為100重量%。Examples of the (meth)acrylic acid alkyl ester include various (meth)acrylic acid alkyl esters described above as components other than styrene constituting the hard segment. Among them, n-butyl (meth)acrylate or 2-ethyl (meth)acrylate is preferred in terms of imparting high touch tack to the resin layer having a tensile elastic modulus of 50 MPa or less. hexyl ester. The ratio of n-butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate in the soft segment of the styrene-acrylic block copolymer is preferably 10% by weight or more. More preferably, it is 20 weight% or more, still more preferably, it is 30 weight% or more, and especially preferably, it is 40 weight% or more, and it can be 100 weight%.
作為上述(甲基)丙烯酸烷基酯，進而，就提高樹脂層之拉伸斷裂應力及斷裂伸長率之方面而言，較佳為包含(甲基)丙烯酸甲酯或(甲基)丙烯酸乙酯。 上述苯乙烯-丙烯酸系嵌段共聚物之軟鏈段中之(甲基)丙烯酸甲酯或(甲基)丙烯酸乙酯之比率較佳為10重量%以上，更佳為20重量%以上，進而較佳為30重量%以上，特佳為40重量%以上。又，較佳為80重量%以下，更佳為70重量%以下，進而較佳為60重量%以下。The alkyl (meth)acrylate preferably contains methyl (meth)acrylate or ethyl (meth)acrylate in order to increase the tensile breaking stress and elongation at break of the resin layer. . The ratio of methyl (meth)acrylate or ethyl (meth)acrylate in the soft segment of the above-mentioned styrene-acrylic block copolymer is preferably 10% by weight or more, more preferably 20% by weight or more, and further It is preferably 30% by weight or more, particularly preferably 40% by weight or more. Furthermore, the content is preferably 80% by weight or less, more preferably 70% by weight or less, and still more preferably 60% by weight or less.
上述樹脂層可被著色。藉由對上述樹脂層進行著色，可賦予雙面黏著帶遮光性。 對上述樹脂層進行著色之方法並未特別限定，例如，可列舉於構成上述樹脂層之樹脂中混練碳黑、氧化鈦等粒子或微細之氣泡之方法、於上述樹脂層之表面塗佈油墨之方法等。The above-mentioned resin layer may be colored. By coloring the resin layer, light-shielding properties can be imparted to the double-sided adhesive tape. The method of coloring the resin layer is not particularly limited. Examples include kneading particles such as carbon black and titanium oxide or fine bubbles into the resin constituting the resin layer, and applying ink to the surface of the resin layer. Methods etc.
上述樹脂層可視需要含有無機微粒子、導電微粒子、塑化劑、黏著賦予劑、紫外線吸收劑、抗氧化劑、發泡劑、有機填充劑、無機填充劑等先前公知之微粒子及添加劑。又，於構成上述第1樹脂層及第2樹脂層之至少一者之樹脂由熱塑性彈性體所構成之情形時，可包含除上述熱塑性彈性體以外之樹脂作為樹脂。The above-mentioned resin layer may optionally contain previously known microparticles and additives such as inorganic microparticles, conductive microparticles, plasticizers, adhesion-imparting agents, ultraviolet absorbers, antioxidants, foaming agents, organic fillers, and inorganic fillers. Furthermore, when the resin constituting at least one of the first resin layer and the second resin layer is composed of a thermoplastic elastomer, a resin other than the thermoplastic elastomer may be included as the resin.
上述樹脂層之厚度並未特別限定，較佳之下限為5 μm，較佳之上限為100 μm。藉由將上述樹脂層之厚度設為該範圍內，本發明之一實施態樣之雙面黏著帶可發揮更優異之二次加工性。就進一步提高二次加工性之觀點而言，上述樹脂層之厚度之更佳之下限為10 μm，更佳之上限為70 μm。The thickness of the above-mentioned resin layer is not particularly limited, but a preferred lower limit is 5 μm and a preferred upper limit is 100 μm. By setting the thickness of the resin layer within this range, the double-sided adhesive tape according to one embodiment of the present invention can exhibit more excellent secondary processability. From the viewpoint of further improving secondary processability, a more preferable lower limit of the thickness of the resin layer is 10 μm, and a more preferable upper limit is 70 μm.
本發明之一實施態樣之雙面黏著帶可視需要具有除上述發泡體基材、上述黏著劑層及上述樹脂層以外之其他層。The double-sided adhesive tape according to one embodiment of the present invention may have other layers in addition to the above-mentioned foam base material, the above-mentioned adhesive layer and the above-mentioned resin layer if necessary.
本發明之一實施態樣之雙面黏著帶之厚度並未特別限定，較佳之下限為0.2 mm，較佳之上限為3 mm。藉由將本發明之一實施態樣之雙面黏著帶之厚度設為該範圍內，可防止雙面黏著帶耐受不住回覆力或反彈力而剝離，實現充分之接著或固定並且發揮優異之二次加工性。就雙面膠帶之剝離抑制及二次加工性之進一步提高之觀點而言，本發明之一實施態樣之雙面黏著帶之厚度之更佳之下限為0.3 mm，更佳之上限為2.8 mm。The thickness of the double-sided adhesive tape according to one embodiment of the present invention is not particularly limited. The preferred lower limit is 0.2 mm and the preferred upper limit is 3 mm. By setting the thickness of the double-sided adhesive tape in one embodiment of the present invention within this range, the double-sided adhesive tape can be prevented from being unable to withstand the restoring force or rebound force and peeled off, thereby achieving sufficient adhesion or fixation and excellent performance. Secondary processability. From the viewpoint of suppressing the peeling of the double-sided tape and further improving the secondary processability, a more preferable lower limit of the thickness of the double-sided adhesive tape according to one embodiment of the present invention is 0.3 mm, and a more preferable upper limit is 2.8 mm.
作為本發明之一實施態樣之雙面黏著帶之製造方法，例如，可列舉如下方法。首先，製造上述發泡體基材與第1樹脂層之積層體，於該積層體上積層第2樹脂層，而形成由第1樹脂層/發泡體基材/第2樹脂層所構成之積層體。 此處，於使用上述苯乙烯-丙烯酸系嵌段共聚物作為構成上述樹脂層之樹脂之情形時，由於樹脂層存在觸黏性，故可容易地積層樹脂層與發泡體基材。又，藉由利用經加溫之貼合機壓接樹脂層與發泡體基材，亦可提高密接性。又，藉由於使基材原料發泡而獲得發泡體基材之步驟時***樹脂層，可進一步提高密接性。又，亦可藉由對用作樹脂層之樹脂片材之表面、或發泡體基材實施表面處理（例如，電漿處理或電暈處理等），而提高樹脂層與發泡體基材之密接性。進而，於樹脂層不存在自黏著性之情形時，可將接著劑層設置於發泡體基材與樹脂層之間而積層。藉由利用作為反應點之羥基或酸基修飾樹脂層之聚合物鏈，亦可提高樹脂層與發泡體基材之密接性。As a method of manufacturing a double-sided adhesive tape according to an embodiment of the present invention, for example, the following method can be cited. First, a laminated body of the above-mentioned foam base material and the first resin layer is produced, and the second resin layer is laminated on the laminated body to form a first resin layer/foam base material/second resin layer. Laminated body. Here, when the above-mentioned styrene-acrylic block copolymer is used as the resin constituting the above-mentioned resin layer, since the resin layer has tackiness, the resin layer and the foam base material can be easily laminated. In addition, the adhesiveness can also be improved by pressure-bonding the resin layer and the foam base material using a heated laminating machine. In addition, by inserting a resin layer during the step of foaming the base material to obtain the foam base, the adhesion can be further improved. In addition, the surface of the resin sheet used as the resin layer or the foam base material can also be subjected to surface treatment (for example, plasma treatment or corona treatment, etc.) to improve the strength of the resin layer and the foam base material. of closeness. Furthermore, when the resin layer does not have self-adhesiveness, an adhesive layer can be provided between the foam base material and the resin layer and laminated. By modifying the polymer chain of the resin layer using hydroxyl groups or acid groups as reaction points, the adhesion between the resin layer and the foam base material can also be improved.
其次，製備形成上述黏著劑層之黏著劑溶液，將該黏著劑溶液塗佈於脫模膜之脫模處理面，將溶液中之溶劑完全乾燥而去除，而形成第1黏著劑層。將該第1黏著劑層以第1黏著劑層與第1樹脂層側對向之狀態重疊於上述由第1樹脂層/發泡體基材/第2樹脂層所構成之積層體之第1樹脂層側之表面。另一方面，準備與上述脫模膜不同之脫模膜，於該脫模膜之脫模處理面塗佈黏著劑溶液，將溶液中之溶劑完全乾燥而去除，藉此，製作於脫模膜之表面形成有第2黏著劑層之積層膜。將所得之積層膜以第2黏著劑層與第2樹脂層側對向之狀態重疊於上述由第1樹脂層/發泡體基材/第2樹脂層所構成之積層體之第2樹脂層側之表面，而獲得由第1黏著劑層/第1樹脂層/發泡體基材/第2樹脂層/第2黏著劑層所構成之積層體。繼而，藉由利用橡膠輥等對所得之積層體進行加壓，而可獲得具有第1黏著劑層/第1樹脂層/發泡體基材/第2樹脂層/第2黏著劑層、且兩黏著劑層之表面由脫模膜所覆蓋之雙面黏著帶。又，於捲繞於輥時，剝下與第2黏著劑層相接之脫模膜，將第2黏著劑層捲繞於內側。此時，與第1黏著劑層相接之脫模膜需要進行雙面脫模處理。Next, prepare an adhesive solution to form the above-mentioned adhesive layer, apply the adhesive solution to the release treatment surface of the release film, and completely dry and remove the solvent in the solution to form the first adhesive layer. The first adhesive layer is overlapped on the first layer of the laminate composed of the first resin layer/foam base material/second resin layer with the first adhesive layer and the first resin layer facing each other. The surface of the resin layer side. On the other hand, a release film different from the above-mentioned release film is prepared, an adhesive solution is applied to the release treatment surface of the release film, and the solvent in the solution is completely dried and removed, thereby producing a release film. A laminated film with a second adhesive layer is formed on the surface. The obtained laminated film is overlapped on the second resin layer of the above-mentioned laminated body composed of the first resin layer/foam base material/second resin layer with the second adhesive layer and the second resin layer facing each other. side surface to obtain a laminate composed of the first adhesive layer/first resin layer/foam base material/second resin layer/second adhesive layer. Then, by pressing the obtained laminated body with a rubber roller or the like, a layer having the first adhesive layer/first resin layer/foam base material/second resin layer/second adhesive layer can be obtained. A double-sided adhesive tape whose surfaces are covered by a release film. Moreover, when winding on a roller, peel off the release film in contact with the 2nd adhesive layer, and wind the 2nd adhesive layer inside. At this time, the release film connected to the first adhesive layer needs to be released on both sides.
本發明之一實施態樣之雙面黏著帶之用途並未特別限定，例如，用於固定可攜式電子機器零件、車載用電子機器零件等。該等用途中之本發明之一實施態樣之雙面黏著帶之形狀並未特別限定，可列舉長方形、邊框狀、圓形、橢圓形、環形等。The use of the double-sided adhesive tape according to one embodiment of the present invention is not particularly limited. For example, it is used for fixing portable electronic device parts, vehicle-mounted electronic device parts, etc. The shape of the double-sided adhesive tape according to the embodiment of the present invention in these applications is not particularly limited, and examples thereof include rectangular, frame-shaped, circular, oval, and ring-shaped.
本發明之一實施態樣之雙面黏著帶就於施加有如回覆力或反彈力之低速剝離應力之狀態下之接著可靠性優異之方面而言，較佳為貼附於階差、角、非平面部等，或用於將零件於變形之狀態下固定。另一方面，由於二次加工性優異，故亦可良好地用於暫時固定之用途。進而，即便於由於某些狀況而貼合後欲剝離之情形時，亦不存在剝離時發泡體基材破裂而殘渣殘留於被黏著體之情況。 本發明之一實施態樣之雙面黏著帶由於可抑制皺褶或折痕之產生並可容易地捲繞成卷狀，故通常可於捲繞成卷狀之狀態下保管，自該卷狀體捲出而使用。The double-sided adhesive tape according to one embodiment of the present invention is preferably attached to steps, corners, and irregular surfaces in terms of excellent adhesion reliability under conditions where low-speed peeling stress such as restoring force or rebound force is applied. Flat parts, etc., may be used to fix parts in a deformed state. On the other hand, since it has excellent secondary processability, it can also be used well for temporary fixing purposes. Furthermore, even if it is necessary to peel off after bonding due to certain circumstances, the foam base material will not be broken during peeling and residue will not remain on the adherend. Since the double-sided adhesive tape according to one embodiment of the present invention can suppress the occurrence of wrinkles or creases and can be easily rolled into a roll, it can usually be stored in a rolled state. The body is rolled out and used.
作為使用本發明之一實施態樣之雙面黏著帶之物品，例如，可列舉：用於TV、監視器、可攜式電子機器等之平板顯示器；可攜式電子機器之相機模組；可攜式電子機器之內部構件；車輛用內飾；家電（例如，TV、空調、冰箱等）之內外飾等。作為本發明之一實施態樣之雙面黏著帶之被黏著體，例如，可列舉可攜式電子機器之側面板、背面面板、各種銘牌、加飾膜、裝飾膜等。 [發明之效果]Examples of articles using the double-sided adhesive tape according to an embodiment of the present invention include: flat panel displays for TVs, monitors, portable electronic equipment, etc.; camera modules for portable electronic equipment; Internal components of portable electronic equipment; vehicle interiors; interiors and exteriors of home appliances (such as TVs, air conditioners, refrigerators, etc.). Examples of adherends of the double-sided adhesive tape according to one embodiment of the present invention include side panels, back panels, various nameplates, decorative films, decorative films, etc. of portable electronic devices. [Effects of the invention]
根據本發明，可提供一種具有優異之應力緩和性及耐衝擊性、兩黏著面之二次加工性優異、且可抑制皺褶或折痕之產生並可容易地捲繞成卷狀之雙面黏著帶。According to the present invention, it is possible to provide a double-sided product that has excellent stress relaxation and impact resistance, excellent secondary processability on both adhesive surfaces, suppresses the occurrence of wrinkles or creases, and can be easily rolled into a roll. Adhesive tape.
以下，列舉實施例對本發明之態樣更詳細地進行說明，然而，本發明並不僅限定於該等實施例。Hereinafter, the aspects of the present invention will be described in more detail with reference to Examples. However, the present invention is not limited only to these Examples.
（鏈轉移劑（RAFT劑）之製造） 將1,6-己二硫醇0.902 g、二硫化碳1.83 g、及二甲基甲醯胺11 mL投入二口燒瓶中，於25℃進行攪拌。向其中以15分鐘滴加三乙胺2.49 g，於25℃攪拌3小時。其次，以15分鐘滴加甲基-α-溴苯乙酸2.75 g，於25℃攪拌4小時。其後，於反應液中添加萃取溶劑（正己烷：乙酸乙酯＝50：50）100 mL及水50 mL，進行分液萃取。將藉由第1次及第2次分液萃取所得之有機層混合，依序利用1M鹽酸50 mL、水50 mL、飽和食鹽水50 mL進行洗淨。於洗淨後之有機層中添加硫酸鈉並進行乾燥後，過濾硫酸鈉，利用蒸發器對濾液進行濃縮，而去除有機溶劑。對所得之濃縮物藉由矽膠管柱層析法進行精製，藉此，獲得RAFT劑。(Manufacturing of chain transfer agents (RAFT agents)) 0.902 g of 1,6-hexanedithiol, 1.83 g of carbon disulfide, and 11 mL of dimethylformamide were put into a two-necked flask, and stirred at 25°C. 2.49 g of triethylamine was added dropwise thereto over 15 minutes, and the mixture was stirred at 25°C for 3 hours. Next, 2.75 g of methyl-α-bromophenylacetic acid was added dropwise over 15 minutes, and the mixture was stirred at 25° C. for 4 hours. Thereafter, 100 mL of extraction solvent (n-hexane: ethyl acetate = 50:50) and 50 mL of water were added to the reaction solution, and liquid separation extraction was performed. The organic layers obtained by the first and second separation extractions were mixed, and washed sequentially with 50 mL of 1M hydrochloric acid, 50 mL of water, and 50 mL of saturated brine. After adding sodium sulfate to the washed organic layer and drying, the sodium sulfate was filtered, and the filtrate was concentrated using an evaporator to remove the organic solvent. The obtained concentrate was purified by silica column chromatography, thereby obtaining a RAFT agent.
（苯乙烯-丙烯酸系嵌段共聚物A之製備） 將苯乙烯（St）84 g、丙烯酸2-羥基乙酯（HEA）3 g、丙烯酸（AAc）13 g、RAFT劑1.6 g、2,2'-偶氮二(2-甲基丁腈)（ABN-E）0.35 g投入反應器中，一面利用氮氣對反應器內進行置換，一面升溫至85℃。其後，於85℃攪拌6小時，進行聚合反應（第一階段反應）。 於第一階段反應結束後，向燒瓶內投入正己烷4000 g，進行攪拌使反應物沈澱，其後，對未反應之單體（St、HEA、AAc）及RAFT劑進行過濾分離，對反應物於70℃進行減壓乾燥，而獲得共聚物（硬鏈段A）。 將由丙烯酸丁酯（BA）100 g、ABN-E0.035 g、及乙酸乙酯50 g所構成之混合物（軟鏈段B）、及之前所得之共聚物（硬鏈段A）投入二口燒瓶中，一面利用氮氣對燒瓶內進行置換，一面升溫至85℃。其後，於85℃攪拌6小時，進行聚合反應，而獲得包含由硬鏈段A及軟鏈段B所構成之苯乙烯-丙烯酸系嵌段共聚物A之反應液。 再者，混合物（軟鏈段B）及硬鏈段A之摻合量設為所得之嵌段共聚物中之硬鏈段與軟鏈段之質量比率為34/66之量。關於所得之苯乙烯-丙烯酸系嵌段共聚物A，將整體設計、硬鏈段設計、及軟鏈段設計示於表1。(Preparation of styrene-acrylic block copolymer A) Mix 84 g of styrene (St), 3 g of 2-hydroxyethyl acrylate (HEA), 13 g of acrylic acid (AAc), 1.6 g of RAFT agent, and 2,2'-azobis(2-methylbutyronitrile) ( ABN-E) 0.35 g was put into the reactor, and while replacing the reactor with nitrogen, the temperature was raised to 85°C. Thereafter, the mixture was stirred at 85° C. for 6 hours to perform a polymerization reaction (first-stage reaction). After the first stage reaction is completed, 4000 g of n-hexane is put into the flask and stirred to precipitate the reactants. Afterwards, the unreacted monomers (St, HEA, AAc) and RAFT agent are filtered and separated, and the reactants are separated. It was dried under reduced pressure at 70° C. to obtain a copolymer (hard segment A). Put the mixture composed of 100 g of butyl acrylate (BA), 0.035 g of ABN-E, and 50 g of ethyl acetate (soft segment B), and the previously obtained copolymer (hard segment A) into a two-necked flask. While replacing the inside of the flask with nitrogen, the temperature was raised to 85°C. Thereafter, the polymerization reaction was performed by stirring at 85° C. for 6 hours, and a reaction liquid containing the styrene-acrylic block copolymer A composed of the hard segment A and the soft segment B was obtained. In addition, the blending amount of the mixture (soft segment B) and the hard segment A is an amount such that the mass ratio of the hard segment and the soft segment in the obtained block copolymer is 34/66. Table 1 shows the overall design, hard segment design, and soft segment design of the obtained styrene-acrylic block copolymer A.
（苯乙烯-丙烯酸系嵌段共聚物B～L之製備） 將整體設計、硬鏈段設計、及軟鏈段設計設為如表1所示，除此以外，以與苯乙烯-丙烯酸系嵌段共聚物A相同之方式獲得包含苯乙烯-丙烯酸系嵌段共聚物B～L之反應溶液。 關於所得之苯乙烯-丙烯酸系嵌段共聚物B～L，將整體設計、硬鏈段設計、及軟鏈段設計示於表1。(Preparation of styrene-acrylic block copolymers B to L) Except that the overall design, hard segment design, and soft segment design were as shown in Table 1, a styrene-acrylic block was obtained in the same manner as the styrene-acrylic block copolymer A. Reaction solution of copolymers B~L. Table 1 shows the overall design, hard segment design, and soft segment design of the obtained styrene-acrylic block copolymers B to L.
（丙烯酸聚合物之製備） 於二口燒瓶中放入乙酸乙酯52重量份，對反應器內進行氮氣置換後，加熱反應器而開始回流。乙酸乙酯沸騰後30分鐘後，投入偶氮二異丁腈0.08重量份作為聚合起始劑。向其中以1小時30分鐘均等且緩慢地滴加由丙烯酸丁酯97重量份、丙烯酸3重量份、丙烯酸2-羥基乙酯0.1重量份所構成之單體混合物，並使其反應。滴加結束30分鐘後，添加偶氮二異丁腈0.1重量份，進而進行聚合反應1小時，一面於反應器內添加乙酸乙酯進行稀釋一面進行冷卻，藉此，獲得固形物成分為40重量%之丙烯酸共聚物之溶液。 相對於所得之丙烯酸共聚物之固形物成分100重量份，添加異氰酸酯系交聯劑（日本聚胺酯公司製造，商品名「Coronate L45」）3.0重量份，進行攪拌，而獲得黏著劑溶液。(Preparation of acrylic polymer) 52 parts by weight of ethyl acetate was put into a two-necked flask, and the reactor was replaced with nitrogen, and then the reactor was heated to start reflux. 30 minutes after the ethyl acetate boiled, 0.08 parts by weight of azobisisobutyronitrile was added as a polymerization initiator. A monomer mixture consisting of 97 parts by weight of butyl acrylate, 3 parts by weight of acrylic acid, and 0.1 parts by weight of 2-hydroxyethyl acrylate was dropped evenly and slowly over 1 hour and 30 minutes, and allowed to react. 30 minutes after the completion of the dropwise addition, 0.1 part by weight of azobisisobutyronitrile was added, and the polymerization reaction was continued for 1 hour. Ethyl acetate was added to the reactor to dilute it while cooling, thereby obtaining a solid content of 40% by weight. % solution of acrylic acid copolymer. 3.0 parts by weight of an isocyanate cross-linking agent (trade name "Coronate L45" manufactured by Nippon Polyurethane Co., Ltd.) was added to 100 parts by weight of the solid content of the obtained acrylic copolymer, and the mixture was stirred to obtain an adhesive solution.
（丙烯酸系嵌段共聚物之製備） 相對於由聚甲基丙烯酸甲酯樹脂所構成之硬鏈段之比率為40重量%、由聚丙烯酸丁酯樹脂所構成之軟鏈段之比率為60重量%、重量平均分子量為60000之可樂麗公司製造之45重量份之LA2270，添加乙酸乙酯100重量份，進行攪拌，而獲得丙烯酸系嵌段共聚物之溶液。 關於所得之丙烯酸系嵌段共聚物，將整體設計、硬鏈段設計、及軟鏈段設計示於表1。(Preparation of acrylic block copolymer) Kuraray has a weight average molecular weight of 60,000 with a ratio of 40% by weight of hard segments made of polymethyl methacrylate resin and 60% by weight of soft segments made of polybutyl acrylate resin. Add 45 parts by weight of LA2270 manufactured by the company to 100 parts by weight of ethyl acetate and stir to obtain a solution of an acrylic block copolymer. Table 1 shows the overall design, hard segment design, and soft segment design of the obtained acrylic block copolymer.
[表1]
（實施例1） （1）第1樹脂層之準備 準備厚度為50 μm之聚對苯二甲酸乙二酯（PET）片材（東麗公司製造，X30）作為第1樹脂層。藉由依據JIS K 7161之方法進行測定，結果，該PET片之拉伸斷裂點應力為180 MPa，拉伸斷裂點伸長率為138%，拉伸彈性模數為4360 MPa。(Example 1) (1) Preparation of the first resin layer A polyethylene terephthalate (PET) sheet (manufactured by Toray, X30) with a thickness of 50 μm was prepared as the first resin layer. By measuring according to the method of JIS K 7161, the tensile breaking point stress of the PET sheet was 180 MPa, the tensile breaking point elongation was 138%, and the tensile elastic modulus was 4360 MPa.
（2）聚乙烯（PE）發泡體基材1之製造 使用低密度聚乙烯（宇部丸善聚乙烯公司製造之「UBE Polyethylene F420」，密度0.920 g/cm3 ）100重量份作為聚烯烴樹脂。將該聚乙烯樹脂100重量份、作為熱分解型發泡劑之偶氮二甲醯胺8重量份、作為分解溫度調整劑之氧化鋅1重量份及作為抗氧化劑之2,6-二第三丁基對甲酚0.5重量份供給至擠出機，於130℃進行熔融混練，而擠出厚度為約0.2 mm之長條片狀之發泡體原片。 其次，向上述長條片狀之發泡體原片之雙面以4.0 Mrad照射加速電壓500 kV之電子束，進行交聯。將交聯後之發泡體原片連續送入至藉由熱風及紅外線加熱器保持於250℃之發泡爐內進行加熱而使其發泡，並一面發泡，一面將MD之延伸倍率設為2.5倍，將TD之延伸倍率設為2.5倍而進行延伸。藉此，獲得厚度為800 μm之由聚乙烯樹脂所構成之發泡體。 依據JISK-6767使用電子比重計（MIRAGE公司製造，「ED120T」）對所得之PE發泡體基材1之密度進行測定，結果為0.07 g/cm3 。進而，藉由依據JIS K 6254進行測定而求出所得之PE發泡體基材1之25%壓縮強度，結果為55 kPa。(2) Production of the polyethylene (PE) foam base material 1 uses 100 parts by weight of low-density polyethylene ("UBE Polyethylene F420" manufactured by Ube Maruzen Polyethylene Co., Ltd., density 0.920 g/cm 3 ) as the polyolefin resin. 100 parts by weight of the polyethylene resin, 8 parts by weight of azodimethylamide as a thermal decomposition foaming agent, 1 part by weight of zinc oxide as a decomposition temperature regulator and 2,6-bistriol as an antioxidant 0.5 parts by weight of butyl p-cresol was supplied to the extruder, and the extruder was melted and kneaded at 130°C to extrude a long sheet-shaped foam original sheet with a thickness of about 0.2 mm. Next, both sides of the original strip-shaped foam sheet were irradiated with an electron beam with an accelerating voltage of 500 kV at 4.0 Mrad to perform cross-linking. The cross-linked foam original sheet is continuously fed into a foaming furnace maintained at 250°C by hot air and infrared heaters for heating and foaming. While foaming, the MD extension ratio is set. is 2.5 times, set the TD stretch magnification to 2.5 times and stretch. Thereby, a foam composed of polyethylene resin with a thickness of 800 μm was obtained. The density of the obtained PE foam base material 1 was measured using an electronic hydrometer (manufactured by MIRAGE, "ED120T") in accordance with JISK-6767, and the result was 0.07 g/cm 3 . Furthermore, the 25% compressive strength of the obtained PE foam base material 1 was measured according to JIS K 6254, and the result was 55 kPa.
（3）第2樹脂層之準備 於苯乙烯-丙烯酸系嵌段共聚物A之乙酸乙酯溶液中摻合相對於苯乙烯-丙烯酸系嵌段共聚物A100重量份為5重量份之交聯劑，將所得者塗敷於表面經實施脫模處理之厚度為50 μm之聚對苯二甲酸乙二酯（PET）片材上，進行乾燥，而獲得厚度為50 μm之未交聯樹脂膜作為第2樹脂層。作為交聯劑，使用日本聚胺酯公司製造之商品名「Coronate L45」。(3) Preparation of the second resin layer The ethyl acetate solution of the styrene-acrylic block copolymer A was mixed with 5 parts by weight of a cross-linking agent based on 100 parts by weight of the styrene-acrylic block copolymer A, and the resultant was applied to the surface. A release-treated polyethylene terephthalate (PET) sheet with a thickness of 50 μm was dried to obtain an uncrosslinked resin film with a thickness of 50 μm as the second resin layer. As a cross-linking agent, the trade name "Coronate L45" manufactured by Nippon Polyurethane Co., Ltd. was used.
於苯乙烯-丙烯酸系嵌段共聚物A之乙酸乙酯溶液中摻合相對於苯乙烯-丙烯酸系嵌段共聚物A100重量份為5重量份之交聯劑，將所得者塗敷於表面經實施脫模處理之厚度為50 μm之聚對苯二甲酸乙二酯（PET）片材上，進行乾燥。其後，於40℃下加熱48小時而使其熱交聯，藉此，獲得厚度為50 μm之第2樹脂膜測定用樣品。 作為交聯劑，使用日本聚胺酯公司製造之商品名「Coronate L45」。 對於所得之第2樹脂膜測定用樣品，藉由依據JIS K 7161之方法進行測定，結果，拉伸斷裂點應力為9.9 MPa，拉伸斷裂點伸長率為388%，拉伸彈性模數為7.6 MPa。 又，對於所得之第2樹脂膜測定用樣品，測定交聯度，結果為50重量%。 進而，利用原子力顯微鏡（AFM，島津製作所公司製造，SPM-9700HT）對所得之第2樹脂膜測定用樣品之表面進行觀察，結果可觀察到柱狀之相分離結構。The ethyl acetate solution of the styrene-acrylic block copolymer A was mixed with 5 parts by weight of a cross-linking agent based on 100 parts by weight of the styrene-acrylic block copolymer A, and the resultant was applied to the surface. Dry on a polyethylene terephthalate (PET) sheet with a thickness of 50 μm that has been released from the mold. Thereafter, the sample was heated at 40° C. for 48 hours and thermally cross-linked to obtain a second resin film measurement sample having a thickness of 50 μm. As a cross-linking agent, the trade name "Coronate L45" manufactured by Nippon Polyurethane Co., Ltd. was used. The obtained second resin film measurement sample was measured according to the method according to JIS K 7161. As a result, the tensile breaking point stress was 9.9 MPa, the tensile breaking point elongation was 388%, and the tensile elastic modulus was 7.6. MPa. Moreover, the crosslinking degree of the obtained second resin film measurement sample was measured, and the result was 50% by weight. Furthermore, the surface of the obtained second resin film measurement sample was observed using an atomic force microscope (AFM, SPM-9700HT manufactured by Shimadzu Corporation). As a result, a columnar phase separation structure was observed.
（4）黏著劑溶液之製備 於具備溫度計、攪拌機、冷卻管之反應器中放入乙酸乙酯52重量份，進行氮氣置換後，加熱反應器而開始回流。乙酸乙酯沸騰後30分鐘後，投入偶氮二異丁腈0.08重量份作為聚合起始劑。向其中以1小時30分鐘均等且緩慢地滴加由丙烯酸丁酯70重量份、丙烯酸2-乙基己酯27重量份、丙烯酸3重量份、丙烯酸2-羥基乙酯0.2重量份所構成之單體混合物，並使其反應。滴加結束30分鐘後，添加偶氮二異丁腈0.1重量份，進而進行聚合反應5小時，一面於反應器內添加乙酸乙酯進行稀釋一面進行冷卻，藉此，獲得固形物成分為40重量%之丙烯酸共聚物之溶液。 對於所得之丙烯酸共聚物，使用Water公司製造之「2690 Separations Model」作為管柱藉由GPC法對重量平均分子量進行測定，結果為71萬。重量平均分子量（Mw）相對於數量平均分子量（Mn）之比（Mw/Mn）為5.5。 相對於所得之丙烯酸共聚物之固形物成分100重量份，添加軟化點為150℃之聚合松香酯15重量份、軟化點為145℃之萜酚10重量份、軟化點為70℃之松香酯10重量份。進而，添加乙酸乙酯（不二化學藥品公司製造）30重量份、異氰酸酯系交聯劑（日本聚胺酯公司製造，商品名「Coronate L45」）3.0重量份，進行攪拌，而獲得黏著劑溶液。(4) Preparation of adhesive solution 52 parts by weight of ethyl acetate was placed in a reactor equipped with a thermometer, a stirrer, and a cooling tube. After nitrogen replacement, the reactor was heated to start reflux. 30 minutes after the ethyl acetate boiled, 0.08 parts by weight of azobisisobutyronitrile was added as a polymerization initiator. A monomer consisting of 70 parts by weight of butyl acrylate, 27 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, and 0.2 parts by weight of 2-hydroxyethyl acrylate was added dropwise evenly and slowly over 1 hour and 30 minutes. mixture and allow it to react. 30 minutes after the completion of the dropwise addition, 0.1 part by weight of azobisisobutyronitrile was added, and the polymerization reaction was continued for 5 hours. Ethyl acetate was added to the reactor to dilute and cooled to obtain a solid content of 40% by weight. % solution of acrylic acid copolymer. The weight average molecular weight of the obtained acrylic copolymer was measured by the GPC method using "2690 Separations Model" manufactured by Water Corporation as a column, and the result was 710,000. The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 5.5. To 100 parts by weight of the solid content of the obtained acrylic copolymer, 15 parts by weight of polymerized rosin ester with a softening point of 150°C, 10 parts by weight of terpene phenol with a softening point of 145°C, and 10 parts by weight of rosin ester with a softening point of 70°C were added. parts by weight. Furthermore, 30 parts by weight of ethyl acetate (manufactured by Fuji Chemical Co., Ltd.) and 3.0 parts by weight of an isocyanate cross-linking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L45") were added and stirred to obtain an adhesive solution.
（5）雙面黏著帶之製造 於第1樹脂層之表面塗佈上述黏著劑溶液，於100℃乾燥5分鐘，藉此，形成厚度為20 μm之黏著劑層。於該黏著劑層上積層PE發泡體基材1，而獲得由第1樹脂層（黏著劑層）/發泡體基材所構成之積層體。 於所得之由第1樹脂層（黏著劑層）/發泡體基材所構成之積層體之發泡體基材側積層未交聯樹脂膜，而形成由第1樹脂層（黏著劑層）/發泡體基材/未交聯樹脂膜所構成之積層體。其次，於40℃加熱48小時而使其熱交聯，藉此，將未交聯樹脂膜製成第2樹脂膜，而獲得由第1樹脂層（黏著劑層）/發泡體基材/第2樹脂膜所構成之積層體。(5) Manufacturing of double-sided adhesive tape The above adhesive solution was applied to the surface of the first resin layer and dried at 100°C for 5 minutes to form an adhesive layer with a thickness of 20 μm. The PE foam base material 1 is laminated on the adhesive layer to obtain a laminate composed of the first resin layer (adhesive layer)/foam base material. An uncrosslinked resin film is laminated on the foam base material side of the obtained laminate composed of the first resin layer (adhesive layer)/foam base material to form the first resin layer (adhesive layer) /Foam base material/Laminate composed of uncrosslinked resin film. Next, the uncrosslinked resin film is made into a second resin film by heating at 40° C. for 48 hours to thermally cross-link it, thereby obtaining the first resin layer (adhesive layer)/foam base material/ A laminate composed of a second resin film.
將上述黏著劑溶液塗佈於厚度為100 μm之經實施脫模處理之由聚乙烯（PE）/道林紙/聚乙烯（PE）所構成之脫模襯墊之脫模處理面，於100℃下乾燥5分鐘，藉此，形成厚度為50 μm之第1黏著劑層。 將上述黏著劑溶液塗佈於厚度為100 μm之經實施脫模處理之由聚乙烯（PE）/道林紙/聚乙烯（PE）所構成之脫模襯墊之脫模處理面，於100℃乾燥5分鐘，藉此，形成厚度為50 μm之第2黏著劑層。Coat the above adhesive solution on the release treatment surface of a release liner composed of polyethylene (PE)/Dolin paper/polyethylene (PE) with a thickness of 100 μm and perform release treatment at 100 Dry at ℃ for 5 minutes, thereby forming a first adhesive layer with a thickness of 50 μm. Coat the above adhesive solution on the release treatment surface of a release liner composed of polyethylene (PE)/Dolin paper/polyethylene (PE) with a thickness of 100 μm and perform release treatment at 100 °C for 5 minutes to form a second adhesive layer with a thickness of 50 μm.
將形成有第2黏著劑層之脫模襯墊以第2黏著劑層與第2樹脂層側對向之狀態重疊於上述由第1樹脂層（黏著劑層）/發泡體基材/第2樹脂層所構成之積層體之第2樹脂層側之表面，而獲得由第1黏著劑層（黏著劑層）/第1樹脂層/發泡體基材/第2樹脂層/第2黏著劑層所構成之積層體。繼而，藉由利用橡膠輥對所得之積層體進行加壓，而獲得具有第1黏著劑層/第1樹脂層（黏著劑層）/發泡體基材/第2樹脂層/第2黏著劑層、且各黏著劑層之表面由脫模襯墊所覆蓋之雙面黏著帶。The release liner with the second adhesive layer formed thereon is overlapped on the above-mentioned structure consisting of the first resin layer (adhesive layer)/foam base material/the second adhesive layer and the second resin layer side facing each other. The surface of the second resin layer side of the laminate composed of two resin layers is obtained by first adhesive layer (adhesive layer)/first resin layer/foam base material/second resin layer/second adhesive layer A laminate composed of agent layers. Then, the obtained laminate is pressed with a rubber roller to obtain a layer having a first adhesive layer/first resin layer (adhesive layer)/foam base material/second resin layer/second adhesive Double-sided adhesive tape with layers and the surface of each adhesive layer covered by a release liner.
（實施例2～8） 使用苯乙烯-丙烯酸系嵌段共聚物B～H作為第2樹脂膜，將第1及第2黏著劑層之厚度設為如表2所示，除此以外，以與實施例1相同之方式獲得雙面黏著帶。(Examples 2 to 8) The same procedure as Example 1 was performed except that styrene-acrylic block copolymers B to H were used as the second resin film and the thicknesses of the first and second adhesive layers were as shown in Table 2. Get double-sided adhesive tape.
（實施例9） （1）聚胺酯（PU）發泡體基材之製造 使用由作為多元醇成分之聚丙二醇（PPG）（重量平均分子量800）90重量份及新戊二醇（分子量800）10重量份、及作為酸成分之ε-己內醯胺所構成之聚酯多元醇（多元醇成分/酸成分摻合比率（重量比）＝8：1）作為多元醇。 於合計100重量份之多元醇中添加胺觸媒（DABCO LV33，SANKYO AIR PRODUCTS公司製造）0.7重量份、泡沫穩定劑（SZ5740M，東麗道康寧公司製造）1重量份，進行攪拌。向其中投入多異氰酸酯（Polymeric MDI，東曹公司製造）而將異氰酸酯指數調整為60。其後，以成為0.2 g/cm3 之方式與氮氣混合攪拌，而獲得混入微細氣泡之溶液。使用敷料器將該溶液以特定之厚度塗佈於厚度為50 μm之PET隔片（Nippa公司製造，V-2）上，使發泡體原料反應，而獲得厚度為800 μm之由聚胺酯樹脂所構成之發泡體（PU發泡體基材）。 依據JISK-6767使用電子比重計（MIRAGE公司製造，「ED120T」）對所得之PU發泡體基材之密度進行測定，結果為0.48 g/cm3 。進而，藉由依據JIS K 6254進行測定而求出所得之PU發泡體基材之25%壓縮強度，結果為33 kPa。(Example 9) (1) Production of a polyurethane (PU) foam base material using 90 parts by weight of polypropylene glycol (PPG) (weight average molecular weight: 800) and 10 parts by weight of neopentyl glycol (molecular weight: 800) as the polyol component Parts by weight and a polyester polyol (polyol component/acid component blending ratio (weight ratio) = 8:1) composed of ε-caprolactam as an acid component were used as the polyol. Add 0.7 part by weight of amine catalyst (DABCO LV33, manufactured by SANKYO AIR PRODUCTS) and 1 part by weight of foam stabilizer (SZ5740M, manufactured by Toray Dow Corning) to a total of 100 parts by weight of polyol, and stir. Polyisocyanate (Polymeric MDI, manufactured by Tosoh Corporation) was added thereto to adjust the isocyanate index to 60. Thereafter, the mixture was mixed and stirred with nitrogen gas to obtain a concentration of 0.2 g/cm 3 to obtain a solution in which fine bubbles were mixed. The solution was applied to a 50 μm thick PET separator (V-2 manufactured by Nippa Corporation) using an applicator to react the foam raw materials to obtain an 800 μm thick polyurethane resin. Composed of foam (PU foam base material). The density of the obtained PU foam base material was measured using an electronic hydrometer (manufactured by MIRAGE, "ED120T") in accordance with JISK-6767, and the result was 0.48 g/cm 3 . Furthermore, the 25% compressive strength of the obtained PU foam base material was measured according to JIS K 6254, and the result was 33 kPa.
（2）雙面黏著帶之製造 於苯乙烯-丙烯酸系嵌段共聚物I之乙酸乙酯溶液中摻合相對於苯乙烯-丙烯酸系嵌段共聚物I100重量份為5重量份之交聯劑，將所得者塗敷於表面經實施脫模處理之厚度為50 μm之聚對苯二甲酸乙二酯（PET）片材上，進行乾燥，而獲得厚度為50 μm之未交聯樹脂膜作為第2樹脂層。作為交聯劑，使用日本聚胺酯公司製造之商品名「Coronate L45」。 於所得之由第1樹脂層/發泡體基材所構成之積層體之發泡體基材側積層未交聯樹脂膜，而形成由第1樹脂層/發泡體基材/未交聯樹脂膜所構成之積層體。其次，於40℃加熱48小時而使其熱交聯，藉此，將未交聯樹脂膜製成第2樹脂膜，而獲得由第1樹脂層/發泡體基材/第2樹脂膜所構成之積層體。 使用所得之由第1樹脂層/發泡體基材/第2樹脂膜所構成之積層體，將第1及第2黏著劑層之厚度設為如表2所示，除此以外，以與實施例1相同之方式獲得具有第1黏著劑層/第1樹脂層/發泡體基材/第2樹脂層/第2黏著劑層、且各黏著劑層之表面由脫模襯墊所覆蓋之雙面黏著帶。(2) Manufacturing of double-sided adhesive tape The ethyl acetate solution of the styrene-acrylic block copolymer I was mixed with 5 parts by weight of a cross-linking agent based on 100 parts by weight of the styrene-acrylic block copolymer I, and the resultant was applied to the surface. A release-treated polyethylene terephthalate (PET) sheet with a thickness of 50 μm was dried to obtain an uncrosslinked resin film with a thickness of 50 μm as the second resin layer. As a cross-linking agent, the trade name "Coronate L45" manufactured by Nippon Polyurethane Co., Ltd. was used. An uncrosslinked resin film was laminated on the foam base side of the obtained laminate composed of the first resin layer/foam base material to form a structure composed of the first resin layer/foam base material/uncrosslinked A laminate made of resin film. Next, the uncrosslinked resin film is made into a second resin film by heating at 40° C. for 48 hours to thermally cross-link it, thereby obtaining a combination of the first resin layer/foam base material/second resin film. Made up of layers. The obtained laminate composed of the first resin layer/foam base material/second resin film was used, and the thickness of the first and second adhesive layers was as shown in Table 2. Otherwise, it was as follows: The first adhesive layer/first resin layer/foam base material/second resin layer/second adhesive layer was obtained in the same manner as in Example 1, and the surface of each adhesive layer was covered by a release liner. Double-sided adhesive tape.
（實施例10） 於苯乙烯-丙烯酸系嵌段共聚物J之乙酸乙酯溶液中摻合相對於苯乙烯-丙烯酸系嵌段共聚物J100重量份為5重量份之交聯劑，將所得者塗敷於表面經實施脫模處理之厚度為50 μm之聚對苯二甲酸乙二酯（PET）片材上，進行乾燥，而獲得厚度為50 μm之未交聯樹脂膜作為第1樹脂層及第2樹脂層。作為交聯劑，使用日本聚胺酯公司製造之商品名「Coronate L45」。 於藉由與實施例9相同之方法所得之發泡體基材之兩側積層未交聯樹脂膜，而形成由未交聯樹脂膜/發泡體基材/未交聯樹脂膜所構成之積層體。其次，於40℃加熱48小時而使其熱交聯，藉此，將未交聯樹脂膜製成第1樹脂膜、第2樹脂膜，而獲得由第1樹脂層/發泡體基材/第2樹脂膜所構成之積層體。 使用如此所得之由第1樹脂層/發泡體基材/第2樹脂膜所構成之積層體，除此以外，以與實施例1相同之方式獲得具有第1黏著劑層/第1樹脂層/發泡體基材/第2樹脂層/第2黏著劑層、且各黏著劑層之表面由脫模襯墊所覆蓋之雙面黏著帶。(Example 10) The ethyl acetate solution of styrene-acrylic block copolymer J was mixed with 5 parts by weight of a cross-linking agent based on 100 parts by weight of styrene-acrylic block copolymer J, and the resultant was applied to the surface. A release-treated polyethylene terephthalate (PET) sheet with a thickness of 50 μm was dried to obtain an uncrosslinked resin film with a thickness of 50 μm as the first resin layer and the second resin layer. . As a cross-linking agent, the trade name "Coronate L45" manufactured by Nippon Polyurethane Co., Ltd. was used. An uncrosslinked resin film was laminated on both sides of the foam base material obtained in the same manner as in Example 9 to form a non-crosslinked resin film/foam base material/uncrosslinked resin film. Laminated body. Next, the uncrosslinked resin film was heated at 40°C for 48 hours to be thermally cross-linked, thereby forming a first resin film and a second resin film to obtain a first resin layer/foam base material/ A laminate composed of a second resin film. Except using the thus-obtained laminate composed of the first resin layer/foam base material/second resin film, a first adhesive layer/first resin layer was obtained in the same manner as in Example 1. /Foam base material/Second resin layer/Second adhesive layer, a double-sided adhesive tape with the surface of each adhesive layer covered by a release liner.
（實施例11） 使用直鏈狀低密度聚乙烯（Exxon Chemical公司製造之「Exact3027」，密度0.900 g/cm3 ）70重量份、直鏈狀低密度聚乙烯（陶氏化學公司製造之「Affinity KC8852」，密度0.875 g/cm3 ，熔點（DSC法）Tm：66℃）30重量份作為聚烯烴樹脂。再者，直鏈狀低密度聚乙烯（陶氏化學公司製造之「Affinity KC8852」）為使用茂金屬化合物之聚合觸媒所得之乙烯-1-辛烯共聚物。又，將發泡劑之重量份變更為7重量份。進而，將MD之延伸倍率變更為2.0倍，將TD之延伸倍率變更為2.0倍。 除上述以外，以與實施例1相同之方式獲得厚度為800 μm之由聚乙烯樹脂所構成之發泡體。 依據JISK-6767使用電子比重計（MIRAGE公司製造，「ED120T」）測定所得之PE發泡體基材2之密度，結果為0.13 g/cm3 。進而，藉由依據JIS K 6254進行測定而求出所得之PE發泡體基材1之25%壓縮強度，結果為91 kPa。 使用PE發泡體基材2作為發泡體基材，使用苯乙烯-丙烯酸系嵌段共聚物K作為第2樹脂膜，除此以外，以與實施例1相同之方式獲得雙面黏著帶。(Example 11) 70 parts by weight of linear low-density polyethylene ("Exact3027" manufactured by Exxon Chemical Company, density 0.900 g/cm 3 ) and linear low-density polyethylene ("Affinity manufactured by Dow Chemical Company" were used) KC8852", density 0.875 g/cm 3 , melting point (DSC method) Tm: 66°C) 30 parts by weight was used as polyolefin resin. In addition, linear low-density polyethylene ("Affinity KC8852" manufactured by Dow Chemical Company) is an ethylene-1-octene copolymer obtained using a polymerization catalyst of a metallocene compound. Furthermore, the part by weight of the foaming agent was changed to 7 parts by weight. Furthermore, the stretching magnification of MD was changed to 2.0 times, and the stretching magnification of TD was changed to 2.0 times. Except for the above, a foam composed of polyethylene resin with a thickness of 800 μm was obtained in the same manner as in Example 1. The density of the obtained PE foam base material 2 was measured using an electronic hydrometer (manufactured by MIRAGE, "ED120T") in accordance with JISK-6767, and the result was 0.13 g/cm 3 . Furthermore, the 25% compressive strength of the obtained PE foam base material 1 was measured according to JIS K 6254, and the result was 91 kPa. A double-sided adhesive tape was obtained in the same manner as in Example 1, except that the PE foam base material 2 was used as the foam base material and the styrene-acrylic block copolymer K was used as the second resin film.
（比較例1） 使用PU發泡體基材作為發泡體基材，使用苯乙烯-丙烯酸系嵌段共聚物L作為第2樹脂膜，除此以外，以與實施例1相同之方式獲得雙面黏著帶。(Comparative example 1) A double-sided adhesive tape was obtained in the same manner as in Example 1, except that the PU foam base material was used as the foam base material and the styrene-acrylic block copolymer L was used as the second resin film.
（比較例2） 使用PE發泡體基材1作為發泡體基材，使用丙烯酸共聚物作為第2樹脂膜，除此以外，以與實施例1相同之方式獲得雙面黏著帶。(Comparative example 2) A double-sided adhesive tape was obtained in the same manner as in Example 1, except that the PE foam base material 1 was used as the foam base material and the acrylic copolymer was used as the second resin film.
（比較例3） 使用PE發泡體基材1作為發泡體基材，使用丙烯酸系嵌段共聚物作為第2樹脂膜，除此以外，以與實施例1相同之方式獲得雙面黏著帶。(Comparative example 3) A double-sided adhesive tape was obtained in the same manner as in Example 1, except that the PE foam base material 1 was used as the foam base material and the acrylic block copolymer was used as the second resin film.
（參考例1） 使用厚度為50 μm之由苯乙烯系三嵌段共聚物M所構成之片材（日本瑞翁公司製造，#3620）作為第2樹脂層，除此以外，以與實施例1相同之方式獲得雙面黏著帶。 再者，苯乙烯系三嵌段共聚物M不具有包含(甲基)丙烯酸烷基酯之嵌段。(Reference example 1) The procedure was obtained in the same manner as in Example 1, except that a sheet made of styrenic triblock copolymer M (manufactured by Japan Zeon Co., #3620) with a thickness of 50 μm was used as the second resin layer. Double-sided adhesive tape. Furthermore, the styrenic triblock copolymer M does not have a block containing alkyl (meth)acrylate.
（評價） 對於實施例、比較例中所得之雙面黏著帶進行以下評價。將結果示於表2。(evaluation) The double-sided adhesive tapes obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 2.
（1）輥捲繞性之評價 將所得之雙面黏著帶（脫模襯墊/第1黏著劑層/第1樹脂層/發泡體基材/第2樹脂層/第2黏著劑層）以第2黏著劑層側為內側之方式捲繞於直徑為3英吋之紙芯，而獲得卷狀體。 藉由目視對所得之卷狀體之側面及表層進行觀察。進而，自卷狀體拉出雙面黏著帶後，自第2黏著劑層側藉由目視進行觀察，根據以下基準進行評價。 〇：於所確認之所有部位未發現皺褶或折痕。 △：於所確認之一部分部位發現皺褶或折痕。 ×：於所確認之所有部位發現皺褶或折痕。(1) Evaluation of roll windability Place the obtained double-sided adhesive tape (release liner/1st adhesive layer/1st resin layer/foam base material/2nd resin layer/2nd adhesive layer) with the second adhesive layer side as the inside In this way, it is wound on a paper core with a diameter of 3 inches to obtain a roll. The side surface and surface layer of the obtained rolled body were visually observed. Furthermore, after the double-sided adhesive tape was pulled out from the roll, it was visually observed from the second adhesive layer side and evaluated based on the following criteria. 〇: No wrinkles or creases were found in any confirmed areas. △: Wrinkles or creases are found in one of the identified parts. ×: Wrinkles or creases are found in all identified areas.
（2）二次加工性之評價 將所得之雙面黏著帶分別切成寬度5 mm×長度100 mm、及寬度10 mm×長度100 mm之大小，而製備5 mm寬之樣品及10 mm寬之樣品。 剝下所得之各樣品之第1黏著劑層側之脫模襯墊，將第1黏著劑層側貼合於厚度為2 mm之玻璃板（寬度50 mm，長度125 mm），利用2 kg之橡膠輥以300 mm/min之速度於雙面黏著帶上往復一次後，於23℃、相對濕度50%之環境下放置24小時。其次，使發泡體基材之層間裂開，自雙面黏著帶去除第2黏著劑層及第2樹脂層、及發泡體基材之一部分後，將雙面黏著帶之殘留之部分以300 mm/min之速度自水平方向拉伸至30°之角度方向，而自玻璃板剝離雙面黏著帶之殘留之部分。對於第1黏著劑層側之二次加工性，根據以下基準進行評價。對於第2黏著劑層側之二次加工性，亦進行相同之評價。 〇：可去除雙面黏著帶之殘留之部分。 △：於剝離中途雙面黏著帶之一部分斷裂，但可去除。 ×：無法去除雙面黏著帶之殘留之部分。(2) Evaluation of secondary processability The obtained double-sided adhesive tape was cut into sizes of width 5 mm × length 100 mm and width 10 mm × length 100 mm, respectively, to prepare 5 mm wide samples and 10 mm wide samples. Peel off the release liner on the first adhesive layer side of each sample obtained, and attach the first adhesive layer side to a glass plate with a thickness of 2 mm (width 50 mm, length 125 mm), and use a 2 kg After the rubber roller reciprocates once on the double-sided adhesive tape at a speed of 300 mm/min, place it in an environment of 23°C and 50% relative humidity for 24 hours. Next, crack the layers of the foam base material, remove the second adhesive layer, the second resin layer, and part of the foam base material from the double-sided adhesive tape, and then remove the remaining part of the double-sided adhesive tape. Stretch from the horizontal direction to the angular direction of 30° at a speed of 300 mm/min, and peel off the remaining part of the double-sided adhesive tape from the glass plate. The secondary processability of the first adhesive layer side was evaluated based on the following criteria. The same evaluation was performed on the secondary processability of the second adhesive layer side. 〇: The remaining part of the double-sided adhesive tape can be removed. △: Part of the double-sided adhesive tape broke during peeling, but it can be removed. ×: The remaining portion of the double-sided adhesive tape cannot be removed.
（3）操作性之評價 將所得之雙面黏著帶切成寬度10 mm×長度220 mm之大小，而製備樣品。 將所得之樣品之上部10 mm利用夾具固定，於下部10 mm安裝夾子。以夾具至夾子間之距離為200 mm之方式分別固定。其次，將200 g之砝碼懸掛於夾子，於懸掛砝碼之狀態下靜置1分鐘後，取下砝碼，測定膠帶之伸長量。關於雙面黏著帶之操作性，根據以下基準進行評價。 ◎：伸長量未達10 mm。 〇：伸長量為10 mm以上。(3) Evaluation of operability The obtained double-sided adhesive tape was cut into a size of 10 mm width × 220 mm length to prepare a sample. The upper 10 mm of the obtained sample was fixed with a clamp, and a clamp was installed at the lower 10 mm. Fix them separately so that the distance between the clamp and the clamp is 200 mm. Next, hang a 200 g weight on the clip, let it stand for 1 minute with the weight hanging, then remove the weight and measure the elongation of the tape. The operability of double-sided adhesive tapes is evaluated based on the following criteria. ◎: The elongation is less than 10 mm. 〇: The elongation is 10 mm or more.
[表2]
（4）固定性評價 對於實施例5、9及參考例1中所得之雙面黏著帶，如以下操作而對固定性進行評價。 首先，準備2片厚度為25 μm之聚對苯二甲酸乙二酯（PET）片材，裁成30 mm×300 mm之大小。將上述實施例（參考例）中所得之雙面黏著帶切成25 mm×200 mm之大小，將所準備之2片PET片材分別貼合於雙面膠帶之雙面，作為測定用試樣。再者，貼合時，以雙面膠帶之一短邊與PET片材之一短邊一致之方式配置，藉此，設置30 mm×100 mm之固持部。於短邊方向上於PET片材之中央配置雙面膠帶。 拿著測定用試樣之固持部，以1000 mm/min之速度相對於雙面膠帶剝離至T字方向（90°方向）。 於使用實施例5及9之雙面黏著帶之情形時，於發泡體之層間發生斷裂。於使用參考例1之雙面黏著帶之情形時，於斷裂前於發泡體與所積層之樹脂片材層之間之界面發生剝離。 [產業上之可利用性](4) Fixedness evaluation Regarding the double-sided adhesive tapes obtained in Examples 5 and 9 and Reference Example 1, the fixability was evaluated as follows. First, prepare two polyethylene terephthalate (PET) sheets with a thickness of 25 μm and cut them into a size of 30 mm × 300 mm. Cut the double-sided adhesive tape obtained in the above example (reference example) into a size of 25 mm × 200 mm, and laminate the prepared two PET sheets to both sides of the double-sided tape respectively to serve as samples for measurement. . Furthermore, when laminating, arrange the short side of the double-sided tape in a manner consistent with the short side of the PET sheet, thereby setting a holding portion of 30 mm × 100 mm. Place double-sided tape in the center of the PET sheet in the short side direction. Hold the holding part of the measurement sample and peel the double-sided tape in the T-shaped direction (90° direction) at a speed of 1000 mm/min. When the double-sided adhesive tapes of Examples 5 and 9 were used, breakage occurred between the layers of the foam. When the double-sided adhesive tape of Reference Example 1 was used, peeling occurred at the interface between the foam and the laminated resin sheet layer before breaking. [Industrial availability]
根據本發明，可提供一種具有優異之應力緩和性及耐衝擊性、兩黏著面之二次加工性優異、且可抑制皺褶或折痕之產生並可容易地捲繞成卷狀之雙面黏著帶。According to the present invention, it is possible to provide a double-sided product that has excellent stress relaxation and impact resistance, excellent secondary processability on both adhesive surfaces, suppresses the occurrence of wrinkles or creases, and can be easily rolled into a roll. Adhesive tape.
1:雙面黏著帶 2:發泡體基材 31:第1黏著劑層 32:第2黏著劑層 41:第1樹脂層 42:第2樹脂層1:Double-sided adhesive tape 2: Foam base material 31: 1st adhesive layer 32: 2nd adhesive layer 41: 1st resin layer 42: 2nd resin layer
圖1係表示本發明之一實施態樣之雙面黏著帶之一例之示意圖。FIG. 1 is a schematic diagram showing an example of a double-sided adhesive tape according to an embodiment of the present invention.
1:雙面黏著帶 1:Double-sided adhesive tape
2:發泡體基材 2: Foam base material
31:第1黏著劑層 31: 1st adhesive layer
32:第2黏著劑層 32: 2nd adhesive layer
41:第1樹脂層 41: 1st resin layer
42:第2樹脂層 42: 2nd resin layer
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| KR20230093413A (en) * | 2020-10-28 | 2023-06-27 | 세키스이가가쿠 고교가부시키가이샤 | adhesive tape |
| JPWO2022244756A1 (en) * | 2021-05-17 | 2022-11-24 | ||
| JP7355096B2 (en) * | 2021-10-05 | 2023-10-03 | Dic株式会社 | Adhesive tape and its manufacturing method, articles using the adhesive tape and its dismantling method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017019951A (en) * | 2015-07-13 | 2017-01-26 | スリーエム イノベイティブ プロパティズ カンパニー | Easily detachable double-sided adhesive tape and application method therefor |
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| JPS56115375A (en) * | 1980-02-15 | 1981-09-10 | Nitto Electric Ind Co Ltd | Rubber foam adhesive tape |
| DE3741251A1 (en) * | 1987-12-05 | 1989-06-15 | Lohmann Gmbh & Co Kg | POLYMER-COVERED FOAM AND METHOD FOR THE PRODUCTION THEREOF |
| JPH0711200A (en) * | 1993-06-29 | 1995-01-13 | Sekisui Chem Co Ltd | Pressure-sensitive adhesive tape |
| JP2002338919A (en) | 2001-05-22 | 2002-11-27 | Sekisui Chem Co Ltd | Rolled material of releasable double-sided pressure- sensitive adhesive tape |
| JP4576095B2 (en) | 2003-04-24 | 2010-11-04 | 東洋インキ製造株式会社 | Double-sided adhesive sheet and abrasive cloth laminate |
| JP2005001261A (en) * | 2003-06-12 | 2005-01-06 | Toyo Tire & Rubber Co Ltd | Adhesive hard polyurethane foam |
| JP2009242541A (en) | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | Impact-absorbing tape |
| JP5249625B2 (en) | 2008-04-15 | 2013-07-31 | 積水化学工業株式会社 | Adhesive sheet for display device front plate |
| JP2009262253A (en) * | 2008-04-23 | 2009-11-12 | Sekisui Chem Co Ltd | Pressure-sensitive adhesion double-coated tape for fixing polishing pad |
| US20130245191A1 (en) * | 2012-03-16 | 2013-09-19 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| DE102012212883A1 (en) * | 2012-07-23 | 2014-05-15 | Tesa Se | Foamed adhesive tape for bonding to non-polar surfaces |
| CN105246996B (en) * | 2013-05-27 | 2018-06-08 | Dic株式会社 | Double-faced adhesive tape |
| JP2014037543A (en) | 2013-10-04 | 2014-02-27 | Nitto Denko Corp | Double-sided adhesive tape |
| DE112015000743T5 (en) | 2014-02-11 | 2016-12-29 | Rogers Corporation | Double-sided adhesive tape, method of manufacture, method of use, and articles assembled therefrom |
| JP6314341B2 (en) | 2014-06-26 | 2018-04-25 | Dic株式会社 | Double-sided adhesive tape and articles |
| WO2016075753A1 (en) * | 2014-11-11 | 2016-05-19 | 株式会社寺岡製作所 | Adhesive tape having foamed resin base material, and method for producing same |
| EP3789466B1 (en) * | 2015-02-27 | 2022-04-13 | 3M Innovative Properties Company | Double coated tape |
| CN110023439B (en) * | 2017-03-29 | 2022-05-24 | 积水化学工业株式会社 | Double-sided adhesive tape |
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2019
- 2019-09-19 CN CN201980055425.3A patent/CN112601795B/en active Active
- 2019-09-19 KR KR1020217000704A patent/KR20210063316A/en not_active Application Discontinuation
- 2019-09-19 JP JP2020548590A patent/JP7377210B2/en active Active
- 2019-09-19 WO PCT/JP2019/036726 patent/WO2020059791A1/en active Application Filing
- 2019-09-20 TW TW108133943A patent/TWI819096B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017019951A (en) * | 2015-07-13 | 2017-01-26 | スリーエム イノベイティブ プロパティズ カンパニー | Easily detachable double-sided adhesive tape and application method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020059791A1 (en) | 2021-09-24 |
| TW202018030A (en) | 2020-05-16 |
| CN112601795B (en) | 2023-06-06 |
| KR20210063316A (en) | 2021-06-01 |
| JP7377210B2 (en) | 2023-11-09 |
| CN112601795A (en) | 2021-04-02 |
| WO2020059791A1 (en) | 2020-03-26 |
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